The fighting broke out just before dawn on Wednesday morning when about 40 National Guard troops moved into the building, Elisio Guzman, director of the Miranda state police, said.
Protesters later threw stones, bottles and Molotov cocktails at troops standing outside the police station.
"We don't agree with the move to take out the state police," Abigail Landaneta, a 41-year-old teacher among the protesters, said.
Opposition officials have repeatedly said that Hugo Chavez, the president, and his administration of trying to take over their areas of control.
Accusing the National Guard of acting like the "militia of a political party", Henrique Capriles, the Miranda state governor, said in a televised news conference that he held the interior minister responsible "because this is a premeditated plan".
Capriles and Chavez's government have launched a series of verbal attacks on each other since the opposition politician defeated a ruling-party candidate in elections last year.
Chavez's government has taken over airports, seaports, highways, hospitals and schools previously controlled by opposition governors and mayors who won elections last year.
The seizures, according to Chavez, are part of a plan to improve public service and clamp down on corruption, but his opponents say it is aimed at undermining them.
The government did not make an immediate response to Wednesday's takeover and clashes.