The Vatican said Pope Francis agreed to meet with the 53-year-old leader because he feels for the Venezuelan people as they endure political, social and economic upheaval at home.
"The meeting took place in the context of the worrying situation ... which the country is going through and which has had severe repercussions on the daily life of the entire population," the Vatican statement said.
"The pope, who has the well-being of all Venezuelans in his heart, wanted to offer his contribution in support of constitutionality in the country and to every step that could help to resolve the open questions and create greater trust between the parties."
Francis is well-versed in South American crises, having served as Cardinal Jorge Mario Bergoglio in his home country of Argentina between 2001 and his election as pope 12 years later.
Maduro made the stop in Rome on his way back from the Middle East, where he lobbied for limits on crude oil distribution in a bid to increase prices and help Venezuela's faltering economy. It was Maduro's first papal visit since both were elected in early 2013.
Over the weekend, opposition lawmakers in Caracas accused Maduro's regime of orchestrating a coup d'etat by postponing a recall effort, and of facilitating the "breakdown of constitutional order."
Maduro has been a controversial world leader, particularly toward the United States, which has only exacerbated Venezuela's ongoing troubles. Monday, the Vatican encouraged Maduro to improve his relations with opposing Venezuelan officials and other nations to find a solution to the crisis.
"[Francis] urged [the parties] to show courage in pursuing the path of sincere and constructive dialogue, to alleviate the suffering of the people, particularly of the poor, and to promote renewed social cohesion, which will allow the nation to look to the future with hope," the Vatican said.
Maduro has a long way to go to get his government back on track. A recent poll found that 75 percent of Venezuelans disapprove of the job he is doing.