The opposition has planned another major demonstration in Caracas on Friday.
US officials said the individual sanctions aimed to show Maduro that Washington would make good on a threat of "strong and swift economic actions" if he goes ahead with a vote on Sunday that critics have said would cement dictatorship in the OPEC country.
A 48-hour general strike is now under way in Venezuela, in protest at the planned vote.
Opponents of President Nicolas Maduro at home and overseas tried again Wednesday to pressure the socialist leader into halting his plans to rewrite Venezuela's constitution, though there was no public sign their efforts were working.
The EU, UN and heavyweight nations in the Organization of American States have all also urged Maduro to drop his controversial plan.
Venezuela's President Nicolas Maduro has lashed out against the United States government after it imposed sanctions on 13 of his regime's top officials, as the South American country's violent anti-government protests have led to more deaths.
The Trump administration hit Venezuela with new sanctions Wednesday targeting 13 current or former top officials in President Nicolas Maduro's government, and threatened more penalties if he goes through with efforts to rewrite the beleaguered country's constitution. Millions took part in a one-day strike from last Wednesday, during which five people died in clashes.
The Colombian flagship carrier is the latest airline to leave the country, further isolating Venezuelans amid widespread unrest and protests.
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What he did to this country and human values, is frightful . We're going to see what is exactly taking place. He said it was a "tough, tough decision".
A defiant Maduro hit back late on Wednesday, holding a campaign style rally where he presented some of those hit by United States sanctions with replicas of a sword belonging to Latin American independence hero Simon Bolivar.
USA officials say the Venezuelan government could face additional sanctions that could hit the country's oil industry.
"The elections are on Sunday, and we really don't know what will happen", Maria de los Angeles Pichardo, who left with her husband and son, told AFP news agency. The oil-rich South American country, which was in the second day of a two-day general strike that shuttered businesses nationwide, has also seen thousands of injuries and arrests.
"The call we've made for the coming days will require each of you to ask yourselves what role you have to play in Venezuela's rescue", said Freddy Guevara, opposition leader and vice president of the National Assembly. They say the use of sectoral candidates, who had to collect signatures and file them to the government-leaning elections council, was a way to weed out anti-government aspirants. "The government of the world?" Rubio has been a strong proponent of sanctions against President Nicolas Maduro's increasingly authoritarian government and its crackdown on the opposition.
"We need to paralyze the whole country", said Flor Lanz, 68, standing with a group of women blocking the entrance to a freeway in upscale east Caracas with rope and iron sheets.
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