Humanitarian aid has become a key focus of the power struggle between Maduro and Guaido, who has been recognized as interim leader by more than 50 countries.
Venezuelan troops have killed at least one person and wounded several others near the Brazilian border, witnesses say, in the first bloodshed linked to opposition efforts to bring aid into the South American country against the wishes of embattled President Nicolas Maduro.
Much like the original 1985 Live Aid concert, which raised funds to relieve the Ethiopian starvation, Branson has set a goal to raise $100 million within 60 days.
Also Saturday, three members of the Venezuelan national guard drove a jeep into barricades at a border crossing with Colombia, saying they wanted sanctuary in the country.
"Days will go by, weeks will go by and Nicolas Maduro the worker's president will continue at the head of the motherland", he added.
Having crossed into Colombia early on Saturday, Guaido briefly boarded one of the trucks as they set off towards the border, carrying 600 tons of nutritional supplements, medicine, and hygiene products into the poverty-stricken country.
Venezuelan troops killed a woman, 42-year-old Zorayda Rodriguez, marking the first fatality since Maduro ordered the closure of Venezuela's land and air borders with neighboring countries, including Brazil, on Wednesday to prevent the entry of US humanitarian aid into the country.
Venezuelans in support of Maduro heeded his request, and began to congregate by the thousands in the country's capital of Caracas to show their support, as his opposition congregates at border crossings. His administration didn't release the list of performers, but Venezuela's Minister of Culture Ernesto Villegas said there were "an infinite number" of artists who were willing to participate.
Some 2.7 million people have fled Venezuela since 2015 amid a devastating political and economic crisis, according to United Nations figures released Friday.
"What we did today, we did for our families, for the Venezuelan people", said one of the four men in a video televised by a Colombian news program, which did not identify them.
Riding by the bridge on his bike, college student Frander Duenas said he hoped to sneak into Colombia to see Branson's Venezuela Aid Live because he's a fan of the musicians performing. Meanwhile aid is being stockpiled in Colombia, Brazil and the Caribbean island of Curacao because of Maduro's ban.
The 35-year-old lawmaker was greeted there by the presidents of Colombia, Chile and Paraguay, three of the nations that have recognised him as interim president.
In a flash the cargo caught fire and, with a black cloud rising above, the activists - protecting themselves from the fumes with vinegar-soaked cloths - unloaded the boxes by hand in a human chain stretching back to the Colombian side of the bridge. The leaders greeted the crowd before the concert ended.
Guaido was in Colombia Saturday seeing off shipments of aid to Venezuela with Colombian president Ivan Duque, reported CBS News. We already know that they are with the people, you have made it very clear to us.
Maduro, who has support from China, Russia and the military high command, accuses the United States of plotting a military intervention.