For Pence, the calls and schedule changes served as the latest example of his supporting role here in place of Trump, who pulled out of the summit so he could manage the USA response to the suspected chemical attack in Syria.
U.S. Commerce Secretary Wilbur Ross leaves after delivering a speech during the Americas Business Summit in Lima, Peru April 12, 2018.
The Mexican president's office said the meeting was proposed by Pence to discuss "the status and outlooks for the bilateral relationship" between the two neighbors.
Jarrod Agen, Pence's deputy chief of staff, said the vice president planned to address the gathering of Latin American leaders about the strikes on Saturday.
Much of Pence's message will be aimed at building support for further isolating Venezuela, which has faced USA sanctions amid a political crisis led by President Nicolas Maduro.
A dozen countries in the region have already been turning up the pressure on socialist Venezuelan President Nicolas Maduro, and are expected to back a statement on the sidelines of the summit condemning the widely-criticized May 20 election.
Recently, U.S. President Donald Trump directed the deployment of National Guard troops to the U.S. -Mexico border to combat illegal migration and drug smuggling. During the meeting with four opposition leaders, Pence listened as they described their once-prosperous country devolving into chaos.
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Opposition leader David Smolansky says Maduro's government "has become a threat to the region".
Despite Trump's absence, US officials sought to use the summit to counter China's rising influence in Latin America and condemn Venezuela's government.
Shortly after arriving, Pence met with Venezuelan opposition figures at the US ambassador's residence in Lima, including the former president of the National Assembly, Julio Borges, and former Caracas Mayor Antonio Ledezma.
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.
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 US policy on Venezuela.
Pence is departing for the Summit of the Americas in Lima on Friday.