According to official data, about four million people already had left Venezuela, the ministry said, noting that inflation was about to reach 1.7 million per cent.
Tensions climbed on January 23 when Guaido declared himself interim president, but Maduro has so far refused calls to step down.
The United States, among some other countries, has recognized Guaido's presidency, and U.S. President Donald Trump has warned that "all options are on the table".
"We condemn the brutality of the Maduro regime, whose socialist policies have turned that nation from being the wealthiest in South America into a state of abject poverty and despair", Trump said.
Venezuelan opposition leader and self-proclaimed interim president Juan Guaido waves to supporters during a rally against Venezuelan President Nicolas Maduro's government in Caracas, Venezuela, Feb. 2, 2019.
"What we have seen in recent weeks, with thousands of people taking to the streets to defy the Maduro dictatorship, is a united people standing as one to say: enough", she said.
He thanked his European Union supporters "for supporting all Venezuelans in this struggle we undertake to rescue our nation's democracy, freedom and justice".
European Union member states had indicated that if no new elections are announced, they would take action within the next few days, including on the issue of recognition of the country's leadership in accordance with Article 233 of the Venezuelan constitution.
The US could attempt to seek the approval of the United Nations Security Council to deliver aid without Mr Maduro's co-operation but Russian Federation would probably block such a move.
President Trump: Democrats do nothing to secure border, national emergency still possible
The address is also being used as a fundraising tool for the President's re-election campaign, soliciting input from supporters. Trump's approval had been sliding in recent weeks, reaching a low of 43 per cent in the Rasmussen poll as the shutdown wore on.
The group built on that backing in its final communique by calling upon "the National Armed Forces of Venezuela to demonstrate their loyalty to the Interim President in his constitutional functions as their Commander in Chief".
Guaido must still find a way to bring in the humanitarian aid given the military's loyalty to Maduro.
"We are preparing to fly in as soon as we get the green light", he said.
Maduro told Italian broadcaster Sky TG24 on Monday that he had sent the letter to the pope "for help in the process of facilitating and reinforcing dialogue".
Maduro has flatly rejected demands for new elections, telling Spanish television he would not "cave in to pressure".
The next Lima Group meeting is due to be hosted by Colombia.
"The United Nations said 40 people were killed in clashes with security forces in a week of protests last month, coinciding with Guaido's self-proclamation as acting leader".
Pope Francis on Tuesday expressed willingness for the Vatican to mediate Venezuela's mounting crisis if both sides seek it. Russia, which along with China has backed Maduro in the crisis, underscored its view that the crisis can be resolved only with negotiations between the government and opposition.