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.
In a sign of possible progress toward that goal, Pence and Mexican President Enrique Pena Nieto scheduled a one-on-one meeting on Saturday.
Jarrod Agen, Pence's deputy chief of staff and communications director, said Pence left the opening ceremony for the Summit of the Americas to place phone calls to Congressional leadership.
The high-level gathering in Lima on Friday and Saturday is expected to focus in part on the crisis in Venezuela and regional measures to further isolate Venezuelan President Nicolas Maduro and his administration. The vice president called Maduro's government a "dictatorship" and said the USA would continue to push a hard line against the country's leadership.
It will be the first meeting between the two leaders.
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 global credit through USA markets or entities.
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Opposition leader David Smolansky says Maduro's government "has become a threat to the region".
Maduro accuses the United States of helping the opposition to undermine his authority by waging what he calls economic "sabotage" in Venezuela. They include National Assembly President Julio Borges and former Caracas mayor Antonio Ledezma.
In the meantime, US Acting Secretary of State John Sullivan held talks with government leaders from Mexico, El Salvador, Guatemala and Honduras while attending the Summit of the Americas in Lima, Peru, Department of State spokesperson Heather Nauert said in a readout.
Pence is filling in for President Donald Trump at the Summit of the Americas in Lima after the president pulled out to focus on the USA response to an apparent chemical weapons attack in Syria. He'll also discuss the influence of Chinese trade in the region.
"Today, we have the president of the United States facing a trade war with China and other countries", Pinera said on a panel at a joint business summit on Friday.
In a series of meetings with Latin American leaders, Pence plans to promote good governance and democratic institutions and urge allies to maintain pressure on Maduro.