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On a night awash in history, Hillary Clinton triumphantly became the first woman to lead a major American political party toward the White House, breaking through a barrier that painfully eluded her eight years ago.

She put an electrifying cap on the Democratic convention’s second night, appearing by video from New York and declaring to cheering delegates, “We just put the biggest crack in that glass ceiling yet.”

Minutes earlier, former President Bill Clinton took on the role of devoted political spouse, declaring his wife an impassioned “change-maker” as he served as character witness. He traced their more than 40-year political and personal partnership in deep detail.

“She has been around a long time,” he acknowledged. Casting her experience as an attribute, he added, “She’s been worth every single year she’s put into making people’s lives better.”

For a man more accustomed to delivering policy-packed stem-winders, Mr. Clinton’s heartfelt address underscored the historic night for Democrats, and the nation. If she wins in November, the Clintons would also be the first married couple to each serve as president.

She will take on Donald Trump, who won the Republican nomination a week ago. Mr. Trump, who campaigned Tuesday in North Carolina, mocked the former president’s speech in advance, calling him “over-rated.”

At Mr. Trump’s convention last week, Ms. Clinton was the target of blistering criticism of her character and judgment, a sharp contrast to the warm and passionate woman described by her husband. Seeking to explain the vastly different perceptions of his wife, Ms. Clinton said simply, “One is real, the other is made up.”

The former president took voters back to a time before an affair with an intern led to his impeachment and to intense public scrutiny of the first couple’s marriage. While her aides believe his past transgressions are old news to voters, they have flared up anew at times during the campaign, with Mr. Trump often leading the charge.

Bill Clinton headlined the second night of the Democratic convention, a jubilant celebration of her formal nomination for president. In an important move for party unity, her primary rival Bernie Sanders helped make it official when the roll call got to his home state of Vermont, prompting delegates to erupt in cheers. It was a striking parallel to the role Ms. Clinton played eight years ago when she stepped to the microphone on the convention floor in Denver in support of her former rival, Barack Obama.

This time, Ms. Clinton shattered the glass ceiling she couldn’t crack in 2008.

She leads a party still grappling with divisions. Moments after Ms. Clinton claimed the nomination, a group of Sanders supporters left the convention and headed to a media tent to protest what they said was their being shut out of the party. At the same time, protesters who had spent the day marching in the hot sun began facing off with police.

Mr. Trump cheered the disruptions from the campaign trail. In North Carolina, he told a convention of the Veterans of Foreign Wars that, “our politicians have totally failed you.”

Indeed, Ms. Clinton’s long political resume secretary of state, senator, first lady has sometimes seemed an odd fit for an electorate deeply frustrated with Washington and eager to rally around unconventional candidates like Mr. Trump and Mr. Sanders. Many voters have questions about her character and trustworthiness, suggesting she’s used her access to power to her personal advantage.

Mr. Clinton spoke after three hours of testimonials from lawmakers, advocates, celebrities and citizens who argued otherwise. Each took the stage to vouch for her commitment to working on health care, children’s issues and gun control.

“Hillary Clinton has the passion and understanding to support grieving mothers,” said Sybrina Fulton, whose son Trayvon Martin was killed in 2012. “She has the courage to lead the fight for commonsense gun legislation.”

The significant time devoted to the testimonials underscored the campaign’s concerns about how voters view Ms. Clinton. Public polls consistently show that a majority of Americans don’t believe she is honest and trustworthy. That perception that was reinforced after the FBI director’s scathing assessment of her controversial email use as secretary of state, even though the Justice Department did not pursue charges.

Mr. Clinton complicated the email controversy last month when he met privately with Attorney General Loretta Lynch in the midst of the FBI investigation. Republicans cast the meeting as a sign that the Clintons play by different rules, while Democrats bemoaned that at the very least, it left that impression.

The former president has campaigned frequently for his wife during the White House race, but mostly in smaller cities and towns, part of an effort by the campaign to keep him in a more behind-the-scenes role. His convention address was his highest profile appearance of the campaign.

Ms. Clinton’s landmark achievement saturated the roll call with emotion and symbols of women’s long struggle to break through political barriers. Jerry Emmett, a 102-year-old woman born before women had the right to vote, cast the ballots for Arizona.

Martha McKenna, a Clinton delegate from Maryland, said the night felt like a celebration for Mr. Sanders’ campaign as well as Ms. Clinton’s. She added, “The idea that I’m going to be here when the first woman president is nominated is overwhelming.”

The Democratic convention drew the party’s biggest stars to sweltering Philadelphia for the week-long event. On Monday night, first lady Michelle Obama made an impassioned case for Ms. Clinton as the only candidate in the presidential race worthy of being a role model for the nation’s children. President Barack Obama and Vice President Joe Biden will speak Wednesday, along with Virginia Sen. Tim Kaine, Ms. Clinton’s new running mate.