Pressure is building on Maduro to step down. The socialist leader has overseen a long economic meltdown, marked by hyperinflation, mounting U.S. sanctions and collapsing oil production.
As a result, some three million Venezuelans have fled abroad over the past five years to escape worsening living conditions.
More than 50 countries, including the U.S. and most Latin American and European countries, have now recognized Guaido as Venezuela's legitimate leader.
It has thrust the oil-rich, but cash-poor, country into uncharted territory — whereby it now has an internationally-recognized government, with no control over state functions, running parallel to Maduro's regime.
"Guaido will continue pushing… to deliver this humanitarian aid in an effort not to lose momentum and also all the regional actors will continue pushing hard on Venezuela because they want to curb, somehow, the migration crisis," Diego Moya-Ocampos, principal political analyst for Latin America at IHS Markit, told CNBC via telephone.
"I think most efforts are now concentrated to make sure that the aid is delivered and to try to establish better logistics so that the Venezuelan people can indeed have access to the food and to medical supplies," he added.