In wrapping a four-country South American tour that began Friday in Chile, Pompeo made a stop in the Colombian city of Cucuta, which is near the border with Venezuela, to meet Venezuelan migrants at a refugee center with Colombian President Ivan Duque.
"I hope that you care," he said in his speech to Maduro. "I hope that you will care enough when you see the horror, when you see the tragedy, to change your ways and to leave your country."
The city of Cucuta is the first step for many of the 3.4 million people who have fled Venezuela due to economic hardships caused by government corruption and soaring inflation.
Pompeo said he expects that number to surpass 5 million by the end of this year as Venezuela struggles with a humanitarian crisis that Maduro has consistently denied.
Maduro's claim to the presidency was declared illegitimate in January following controversy over his re-election. National Assembly Leader Juan Guido declared himself interim president and has the support of some 50 countries, including the United States. But Maduro has held tight to the reigns of power, claiming the attempt to dethrone him is a U.S.-backed coup.
The situation has worsened in Venezuela amid the struggle for power with the country repeatedly suffering massive power outages, which caused Maduro to institute electricity rationing this month.
The United States has provided over $200 million in aid to Venezuela but has had trouble getting it into the country, Pompeo said.
"Nicolas Maduro refused to accept it," he said. "He refuses to allow this aid to get across."
In mid-February, Maduro closed its borders with Brazil and Colombia as volunteers prepared to bring aid into the country. Two people were killed during a firefight at a Brazil border crossing as Venezuelan troops loyal to Maduro opened fire.
Pompeo then called on Venezuelans the world over to reject Maduro's claim to power and that the United States will continue to explore further diplomatic and economic maneuvers to aid in his removal.
Duque reaffirmed his commitment to helping the United States and said he hopes Maduro will one day be charged in international criminal court and convicted for "the terrible crimes that he has committed."
"Today, we are giving a clear message to the Venezuelan people: We are with you to defeat dictatorship," he said. "We are with you for you to recover your freedom."