Poly(vinyl acetate) films containing benzophenone were photocrosslinked by continuous UV irradiation.UV irradiation of PVAc film containing 5% benzophenone induced bulk crosslinking of the polymer indicated by 84.1% of gel fraction after ethyl acetate extraction. The crosslinking was attributed to the recombination of tertiary polymer radicals generated upon UV irradiation, which was enhanced by the hydrogen abstraction of benzophenone. Also the UV irradiation resulted in scission of ester linkage and photooxidation of PVAc surface, which was verified by ATR and zeta potential analysis, implying that the PVAc surface became more polar and hydrophilic. The zeta potential proportionally increased from +4.5mV to -26.8 mV with increasing UV irradiation. Also the surface energy of the PVAc film increased with higher UV irradiation upto 56.5 $mJ/m^2$ by the enhanced Lewis acid/base component with larger contribution of Lewis acid parameter. Accordingly the crosslinked PVAc showed higher thermal stability with increasing UV energy.