They say Argenis Hernandez was shot in the stomach on Friday in the city of Valencia and later died in hospital.
Also on Friday, bus driver Wilfredo Rey died after being shot by a group of hooded gunmen in San Cristobal.
At least 33 people have now been killed during weeks of protests over the high inflation and basic good shortages.
Meanwhile, supporters and opponents of the president staged rival rallies in the capital Caracas on Saturday.
This comes a day after riot police in the city  clashed with anti-government demonstrators who were protesting against the arrest of two opposition mayors.
The mayors were detained over their alleged role in the unrest.
The opposition says the government is violently repressing the protests and trying to silence the administration's critics.
President Maduro has blamed the violence on "fascist groups", accusing them of planning a coup against his government.
He says he has repeatedly invited them to the presidential palace for talks, but that they have refused to attend.
Opposition leader Henrique Capriles said he accepted the invitation but is yet to meet Mr Maduro.
Two people have died from gunshot wounds during protests against President Nicolas Maduro's government, eyewitnesses and local media say.