N-Vinylformamide (NVF) free-radical polymerization was found to form polymer gels at high conversions both in bulk and in solution. the polymerization was conducted at different temperatures, monomer and initiator concentrations to show the gelation conditions. Gel fractions and gel swelling ratios were also measured after separating the gel from the polymer samples. In order to confirm the crosslinking unit, a series of hydrolysis experiments were conducted on the gel samples. The hydrolysis results showed that the crosslinks in PNVF gels could be destroyed by alkaline hydrolysis. The most appropriate explanation to this fact is that crosslinking takes place via the amide group.