Former presidential candidate Henrique Capriles said 85 officers, a majority from the military, had been detained for "expressing discontent" with the actions of the nation's National Guard.
Capriles said he received information about the detained officers through some of their relatives, who indicated they wanted their position shared with the public.
There has been no independent confirmation of the detentions.
National guardsmen have repeatedly launched tear gas and rubber bullets in more than a month of anti-government protests. Demonstrators are calling for President Nicolas Maduro to hold elections, but the embattled leader shows no sign of ceding to their demands, AP reported.
Authorities announced Friday that Hecder Lugo, 20, had died a day after being shot in the industrial city of Valencia, which has been the scene of ongoing protests and massive looting.
His death brought to at least 38 the number of people reported dead by various sources, though the public prosecutor puts the tally at 37. More than 700 others have been injured.
Opposition leaders have repeatedly called on officers to think with their conscience before launching attacks, noting that among the protesters could be their own relatives and friends.
The opposition is calling for women to march throughout the nation Saturday, while pro-government women's groups are planning a counter-demonstration.