Gelation of crosslinking polymers, with ionic groups, is of interest in membrane processing of these materials. The gelation of polyvinyl alcohol in the presence of an ionic crosslinker, sulfosuccinic acid, was monitored through rheological measurements. The evolution of rheological material functions during film formation, which involves solvent evaporation and crosslinking, was observed at different polymer and crosslinker concentrations. Relative effect of water evaporation leading to physical gelation and the chemical crosslinking was examined. To understand the effect of crosslinker type, the rheology of nonionic crosslinker, glutaraldehyde was also examined. The gel points as well as network parameters for these covalent networking systems were different and depended on crosslinker type and polymer/crosslinker concentrations. However, qualitative evolution of rheological behavior during film formation was largely similar, demonstrating the dominating effect of solvent evaporation. Crosslinking in the absence of solvent evaporation was examined at different temperatures. It can be concluded that similar mechanism was involved, independent of temperature, in the temperature range of interest. The effect of crosslinker concentration on evolution of rheological properties near gelation was insignificant for ionic crosslinker though marginally significant for nonionic crosslinker.