The coastguard said an entire bay on the southeast of the island had been affected after the Agia Zoni II carrying 2.5 metric tonnes of fuel sank.
The spill extends over 1.5 kilometres and the full cleanup will likely require four months, greater Athens fisheries councillor Voula Toutountzi told the capital's municipal radio.
It was not immediately clear what caused the sinking late on Sunday. Weather conditions in the area were mild at the time.
The tanker's captain and chief engineer were charged with negligence and released pending trial.
The coastguard said barriers had been erected to contain the spill and tanker trucks were being used to collect the oil. But much of the fuel ended up on Salamina's beaches regardless.
Efforts to plug the breach in the tanker's hull are ongoing.
Local officials said fishermen had been told to avoid the area.
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