Shortly after arriving, Pence met with Venezuelan opposition figures at the USA ambassador's residence in Lima, including the former president of the National Assembly, Julio Borges, and former Caracas Mayor Antonio Ledezma. The vice president spoke to top Republican and Democratic leaders from his hotel suite before attending a banquet hosted by Peruvian President Martin Vizcarra.
"We want one message to be clear: We are with the people of Venezuela", Pence said at the USA ambassador's residence, seated with a group of Venezuelan opposition leaders.
In a sign of possible progress toward that goal, Pence and Mexican President Enrique Pena Nieto scheduled a one-on-one meeting on Saturday.
Pence urged the extra measures as he met with Venezuelan opposition figures in Lima who called for more sanctions and "intervention" in their crisis-hit country.
The United States already has sanctions in place against Maduro and his top officials, as well as other measures preventing the teetering Venezuelan government and state oil company from accessing worldwide credit through U.S. markets or entities.
Pence was filling in for US President Donald Trump, who cancelled his trip to the summit to watch over America's response to a suspected poison gas attack in Syria.
But some business and political leaders gathered in Lima for the summit said Trump's message on Latin America, and trade, was confusing.
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While Trump himself was silent on Syria on Friday , giving no further clues on whether American military action is imminent, U.S. Russia's envoy Nebenzia called on the United States, France and Britain "not to bring the world to such a unsafe threshold".
A Pence aide said Pence planned to meet with Pena Nieto early Saturday, with the get-together only being finalized late on Friday.
It will be the first meeting between the two leaders.
Trump had been scheduled to attend the Americas summit but decided this week to send Pence instead so he could remain in the United States to focus on formulating a US response to a suspected chemical weapons attack in Syria last weekend.
In meetings with Latin American leaders, the vice president is expected to promote good governance and democratic institutions.
Ana Quintana, a senior policy analyst on Latin America and the Western Hemisphere for the Heritage Foundation, said Pence would seek to "continue the momentum" of USA policy on Venezuela.
Pence will also aim to counter China's attempt to exert more economic influence in the Americas at a time when the Trump administration has been embroiled in a trade dispute with the Chinese.