Small angle light scattering (SALS) and field emission scanning electron microscope (FE-SEM) have been used to investigate the effects of alcohol on phase separation of chlorinated poly(vinyl chloride) (CPVC)/tetrahydrofuran (THF)/alcohol (9/61/30 wt%) solution during water vapor induced phase separation. A typical scattering pattern of nucleation & growth (NG) was observed for all casting solutions of CPVC/THF/alcohol. In the case of the phase separation of CPVC dope solution containing 30 wt% ethanol or n-propanol, the demixing with NG was observed to be heterogeneous. Meanwhile, the phase separation of CPVC dope solution with 30 wt% n-butanol was found to be predominantly homogeneous NG. Although the different phase separation behavior of NG was observed with types of alcohol additives, the resultant surface morphology had no remarkable differences. That is, even though the NG process by water vapor is either homogeneous or heterogeneous, this difference does not play a main role on the final surface morphology. However, it was estimated from the result of hydraulic flux that the phase separation by homogeneous NG provided the membrane geometry with lower resistance in comparison with that by heterogeneous one.