A method is provided for recovering poly(arylene sulfide) from a liquid reaction mixture, comprising a liquid-phase poly(arylene sulfide) and a polar organic compound which can also function as a solvent for the polymer, and water. The liquid reaction mixture is contacted by an amount of a vaporized phase separation agent at least sufficient to effect or enhance a phase separation of the liquid-phase poly(arylene sulfide) component from the polar organic compound. The poly(arylene sulfide resins recovered according to this invention exhibit greater particle size than those recovered according to prior art methods, and do not tend to adhere to vessel walls during recovery.