With political and social chaos mounting, this week's deaths bring to 106 the number of people killed in the latest round of anti-government protests, which started four months ago.
The prosecutor's office says Rafael Antonio Vergara was slain in the town of Ejido, outside the city of Merida, without offering further details.
A two-day general strike was organized by the opposition in defiance of the vote.
What the protesters want now, Bloomberg's Andrew Rosati told Morning Edition from Caracas, is to halt the impending constituent assembly: "And on top of that, the main demand from the opposition is a new round of free and fair elections".
Sanctions prohibiting any transaction in USA currency by PDVSA, for instance, are among the toughest of various oil-related measures under discussion at the White House, a senior White House official and an adviser with direct knowledge of the discussions told Reuters last week.
Venezuelan opposition leaders have called a two-day general strike beginning Wednesday to protest Maduro's plans to rewrite the country's constitution.
He warned that anybody elected to the Constituent Assembly could also face U.S. sanctions.
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Lashing out against the United States, Venezuela's leader Maduro called the new U.S. sanctions against people from his regime "illegal, insolent and unprecedented", as cited by AFP. Their goal: For Maduro to abandon his plans for a new constitution, opposition leaders said at a news conference. "They are few, but they have the weapons and the money", said decorator Cletsi Xavier, 45, helping block the entrance to a freeway in upscale east Caracas with rope and iron metal sheets.
Venezuela's government today sought to quash deadly protests against a controversial weekend election, issuing a ban that sharply intensifies a showdown over President Nicolas Maduro's widely panned plan to rewrite the constitution.
"The elections are on Sunday and we really don't know what will happen", said one, Maria de los Angeles Pichardo, who left with her husband and son.
The opposition has planned another major demonstration in Caracas on Friday.
Maduro accused the USA of fomenting the unrest against him and his government, with the help of the conservative opposition. The government in Brasília has floated the idea of hosting peace talks between the Venezuelan government and opposition under the auspices of regional trade bloc Mercosur, of which it holds the rotating presidency.
"They try to question the humanity of the other side as a political tactic, and I think that ends up discouraging and dismaying people", said David Smilde, a Tulane University expert on Venezuela. "The government of the world?" he said. Former Spanish Prime Minister Jose Luis Rodriguez Zapatero has spoken with the opposition and with ruling Socialist Party officials about postponing the constituent assembly election, according to three opposition sources. He calls on Venezuelans "to stop this with peaceful resistance and deep commitment to our efforts".
Nations including Argentina, Brazil, Mexico, the United States and Canada said the vote amounted to a "dismantling of democratic institutionality". "I ask you not to be accomplices in the annihilation of the republic".