Vance's visit, which also includes a meeting with the pope's right-hand man, comes a day after Meloni met President Donald Trump in Washington in a brief trip aimed at discussing a potential EU-US trade deal.
Trump's threatened tariffs could have a major impact on Italy, which sends around 10 percent of its exports to the United States.
The Rome visit marks Vance's first trip to Europe since delivering a combative speech at the Munich Security Conference in February, when he urged the bloc to "step up" in managing its own security.
Vance said on X that he had a "great meeting" with Italy's premier Giorgia Meloni, a conservative leader who shares many of his views.
"I'm grateful every day for this job, but particularly today where my official duties have brought me to Rome on Good Friday," Vance said.
In brief comments to the press ahead of his meeting, Vance said he would update Meloni on trade negotiations with the European Union.
He added that he would also brief the premier on negotiations involving Ukraine, as well as "some of the things that have happened in the past 24 hours".
"We do feel optimistic that we can hopefully bring this war, this very brutal war, to a close," he said.
His statement appeared to contradict more sceptical comments from Secretary of State Marco Rubio, who said on Friday that the United States was prepared to "move on" should peace not be "doable in the short term".
Vance, his wife and three children attended the Celebration of the Passion of the Lord at St Peter's Basilica later on Friday.
Following the two-hour service, the family was given a private tour of Castel Sant'Angelo – the former mausoleum of Roman emperor Hadrian which the church later converted into a fortified castle.
Vance is scheduled to speak with Cardinal Pietro Parolin – the second-highest official at the Holy See after Pope Francis – on Saturday.
Vance, who converted to Catholicism in his mid-30s, also plans to attend Easter mass in St Peter's Square on Sunday.
‘Making the West great again’
Meloni was the first leader from Europe to visit Trump since he imposed 20-percent tariffs on EU exports, which he has since suspended for 90 days.
The two leaders met in the Oval Office on Thursday, with Trump hailing the 48-year-old Italian premier as "fantastic".
Meloni, who has positioned herself as the only European leader capable of de-escalating Trump's trade war, highlighted their conservative common ground and said she wanted to "make the West great again".
While Trump expressed confidence about a trade deal with the EU, he said that he was in "no rush" to reach an agreement.
READ ALSO: Trump says he’s ‘100 percent’ sure of EU-US trade deal as Italy's Meloni visits
Russia's war in Ukraine remained a delicate subject between Trump and Meloni.
The Brothers of Italy leader has been a staunch ally of Ukraine and President Volodymyr Zelensky since Russia's invasion in 2022, recently calling Moscow's Palm Sunday attack on the city of Sumy "horrible and vile".
Since taking office in January, Trump has stunned allies with a foreign policy pivot towards Moscow and repeated attacks on Zelensky.
The US leader said on Thursday: "I don't hold Zelensky responsible but I'm not exactly thrilled with the fact that that war started."
He also said he wasn't "a big fan" of the Ukrainian leader.
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