Maduro accused Spanish Prime Minister, Pedro Sanchez, of having taken "a bad decision" in recognising Guaido.
Guaido has won backing from the United States, European powers including France, Germany and Spain, Canada, Australia and a dozen Latin American countries to take over the leadership, but Russian Federation and China continue to support Maduro.
"We are not beggars", Maduro said in a speech to troops broadcast on Venezuelan state TV.
Prime Minister Justin Trudeau and Foreign Affairs Minister Chrystia Freeland branded the Maduro government a dictatorship that has shown an inexcusable disregard for the rule of law and human rights. According to United Nations statistics, as many as 208,300 Venezuelans have arrived in Spain.
Plea for help comes after nations recognise country's rival opposition chief as interim leader.
French President Emmanuel Macron tweeted he backs Guaido as the "acting president to implement an electoral process". "Venezuelans have the right to express themselves freely and democratically", he wrote on Twitter.
At least three million people have fled Venezuela since 2015.
"We want to see free and fair elections for the people to make a democratic decision in Venezuela", Irish Foreign Minister Simon Coveney said.
"We are looking at what further steps we can take to ensure peace and democracy in Venezuela, including through sanctions".
Meanwhile Guaido, already recognized by the US, Canada, Australia and several Latin American countries, said he would soon lobby the European Union for badly-needed humanitarian and economic aid.More news: Qatar stun Japan to win first Asian Cup
Maduro has rejected all offers of aid, dismissing it as the thin edge of a wedge of U.S. military involvement.
Monday's declaration came after Guaido made a larger-than-life appeal to Canada and its Western Hemisphere partners to end the "usurpation" of democracy in his country.
The 35-year-old lawmaker, who is the head of the South American country's National Assembly, declared himself Venezuela's interim head of state last month, directly challenging Maduro's claim to the presidency.
"I told him that I serve Christ's cause... and in this spirit I asked for his help, in a process of facilitating and strengthening dialogue", said Maduro, who has rejected calls for snap presidential elections.
The Government, it said, will "completely revise bilateral relations with those countries from now on".
Venezuelan opposition leader Juan Guaido walks at the National Assembly before a news conference in Caracas, Venezuela February 4, 2019.
"I call to reject intervention", he said, urging the soldiers to defend the country against "Yankee imperialism".
"Handing out ultimatums, sanctions, freezing Venezuelan goods..."
He began to exercise authority for the first time this weekend, calling on the army to allow in humanitarian aid to a nation wracked by economic crisis.
US Secretary of State Mike Pompeo and Deputy Head of European Diplomacy Helga Schmid were to participate by videoconference in the debates.
"The unity of positions in the modern and most influential foreign powers leaves Maduro isolated and weakened, and it strengthens Guaido's leadership internally", said Luis Vicente Leon, a political analyst and director of the Datanalisis polling agency.
Russian Federation and China, who have poured billions of dollars of investment and loans into Venezuela, are supporting Mr Maduro in an extension of their geopolitical tussle with the United States. Several of Washington's Latin American allies followed suit.