The former bus driver rose through the political ranks with his faithful support of the late President.
More than 20 world leaders are expected to attend the funeral today, but there will be no burial as he will be embalmed.
Thousands flocked to the streets of Caracas to see the coffin of Chavez travel through the city to lie in state until Friday's funeral.
The British man who was shot dead on Monday in Venezuela "loved" his adopted country, but had narrowly escaped death in a similar incident in 2000, his friend and business partner Luis Dominguez said in an interview.
Thomas Henry Berry and his ex-wife were killed in front of their five-year-old daughter when their car broke down on a highway.
A former Miss Venezuela and her British ex-husband were shot dead after their car broke down in the country on Monday night.
Their 5-year-old daughter survived the attack but was left with a bullet wound in her leg.
ITV News Correspondent Neil Connery reports.
A former Miss Venezuela and her British ex-husband were shot dead after their car broke down in the country on Monday night. Their 5-year-old daughter survived the attack but was left with a bullet wound in her leg, the government and local media said.
Monica Spear, 29, who was also a soap opera actress, and Henry Berry, 39, died in an attempted robbery on the highway between Puerto Cabello and Valencia in central Venezuela.
The 2004 Miss Venezuela winner lived in the United States but was vacationing in her homeland.
The Foreign Office said they are, "aware of the death of a British national" and are providing consular assistance.
President Nicolas Maduro has been granted powers to rule by decree for a year, it was announced tonight.
The President said he needed the powers to fix the economy, but adversaries regard this as a power grab.
Maduro now has the power to pass laws without the approval of the Venezulan congress or a second democratic party.
Speaking to a crowd of supporters after the victory, Maduro said: "I want to thank the majority of patriotic and socialist lawmakers for approving this law that will let us advance, over the next 12 months, in defeating the economic war being waged against our people.
"Tonight has been a victory for the people! ... Who says the revolution is over?" he added, flanked by ministers, to applause from a crowd outside the Miraflores presidential palace.
Maduro, who showed a photo of a white-plaster wall with marks that appear like eyes and a nose, said Chavez's face had briefly appeared to workers building a new subway line in Caracas in the middle of the night.
Speaking on state television, the president said: "My hair stands on end just telling you about it. Who is that face? That gaze is the gaze of the fatherland that is everywhere around us, including in inexplicable phenomena."
Maduro - who was elected president in April after the death of Chavez - has previously spoken of seeing the spirit of his idol several times, including in the shape of a bird.
The US fugitive Edward Snowden has accepted an offer of asylum from Venezuela, according to the AFP news agency.
A lawmaker close to the Kremlin, Duma politician Alexey Pushkov, tweeted that Mr Snowden has accepted an offer of asylum.
A man in a red jacket ran onto the stage during Venezuelan President Nicolas Maduro's inauguration speech today and grabbed the microphone, but was quickly tackled by his bodyguards.
"The security has failed totally. They could have shot me easily," Maduro said after resuming his speech to an audience that included the leaders of Brazil, Iran and Argentina.
Venezuela's electoral authority is to carry out a full audit of electronic votes cast in the country's presidential election.
The announcement, reported by Reuters, comes hours before Nicolas Maduro was due to be sworn in as Hugo Chavez's successor after a narrow victory on Sunday.
The US had already called for a recount of the closely fought poll.
Mr Maduro was declared the winner by the country's National Electoral Council by 262,000 votes from 14.9 million cast by Venezuelans.
Fireworks have been let off in Caracas as Venezuela elected Nicolas Maduro as president - opposition backers banged pots and pans in reaction to the vote result.
Venezuela's ruling party candidate Nicolas Maduro called for peace and said he would be willing for Sunday's election result to be audited after officials said he took 50.76 percent of votes, compared to 49.07 percent for his rival Henrique Capriles.
"We don't want violence, we want peace," Maduro said in a speech to the nation.
"They [the opposition] want an audit, we welcome the audit ... I formally request the National Electoral Commission to carry out an audit."