While the names of the prisoners have yet to be officially published, or even revealed to ministers, they reportedly include militants convicted of killing Israeli women and children or Palestinians suspected of collaborating with Israel.
An unofficial list published by Almagor, a group representing Israeli victims of Palestinian attacks, said that candidates for release also included those jailed for acts such as the killing of a creditor, murder during car theft and a man convicted of strangling his wife whom he suspected of adultery.
The planned releases have brought protests from Israeli victims' families and from Netanyahu's hardline coalition partners.
Israeli media reported on Sunday that the far-right Jewish Home party intends to vote against the plan, while the equally hardline Yisrael Beitenu had given its ministers a free vote.
There were rumblings within Netanyahu's own right-wing Likud party too, with deputy defence minister Danny Danon urging the party's ministers to vote "no" in Sunday's cabinet session, which begins at 0700 GMT.
Commentators nevertheless expected Netanyahu to win the vote, albeit by a narrow margin.
A Palestinian official told AFP on Saturday that the US-brokered renewal of peace talks, stalled since September 2010, would open in Washington on Tuesday.
Qadura Fares, head of the Palestinian Prisoners' Club which tracks the well-being of Palestinians in Israeli jails, said on Sunday that there would be no talks unless all 104 prisoners returned to their homes.
"If they don't free all of them, there will be no negotiations," he told Israeli public radio.
In past deals, Israel has expelled some freed prisoners from the occupied West Bank or annexed east Jerusalem to the Gaza Strip or abroad but Fares said that would not be acceptable this time.
"Expulsion is punishment," he said. "These people. who are now over 50 years old, all of them sick, need to be released to their homes."