The mob shouted "fascists, fascists" as they demanded the release of supporters arrested on Friday, when 42 people were killed in Ukraine's worst day of violence since its revolution.
Militants chanted "Russians won't abandon their own" as they smashed windows and broke down the gate at the police compound.
Odessa officers said 67 activists were allowed to walk free.
Ukraine's interim Prime Minister Arseniy Yatsenyuk, who was visiting the city on Sunday, told Sky News his country is facing a "well-planned and well-plotted" Russian operation.
"It seems to me that the entire world is facing a new type of war," he said.
"This is the new war, with the military, with no insignia on their uniforms, with agents that have a well-organised terrorist plot network.
"With the diplomatic pressure on Ukraine, with the tough and rude Russian propaganda, with playing on Ukrainian sentiments and not only Ukrainian.
"And with the real threat to the global security and mainly to the European one."
Elsewhere, the Ukrainian government said its armed forces had reclaimed a television tower in Kramatorsk.
Insurgents torched buses in the city on Saturday in an effort to ward off attacks.
Russian television claims 10 people have already died in the violence.
Armed personnel carriers were seen driving through Kramatorsk on Saturday but appeared to later return to their airfield base on the edge of the city.
Rebels have seized government buildings in around a dozen cities in eastern Ukraine as they push for autonomy from Kiev.
The deadly fire in Odessa on Friday pushed tensions to a new high.
At least 31 pro-Russian activists died when a trade union building was petrol-bombed during fighting with groups loyal to Kiev.
Russia said it was "outraged" and denounced the "criminal irresponsibility" of the pro-Western authorities in Kiev.
Sky's Katie Stallard, in Odessa, said people are still bringing flowers to lay outside the building during a second day of official mourning.
"There are real fears about where this goes from here," said Stallard.
"There is already talk of pro-Russian separatists publishing names and contact details of who they say are pro-Ukrainian protesters, who they accuse of being involved in the violence."
Sky news
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