Novel photocrosslinkable second-order nonlinear optical(NLO) polymers were synthesized from radical homopolymerization of 4-[N-ethyl-N-(2-methacryloyloxyethyl)]amino-4’-(2-cinnamoyloxyethyloxycarbonyl)-2’-nitroazobenzene(MACN) or copolymerization of MACN with 2-(cinnamoxyloxy)ethyl methacrylate(CM), and from polycondensation of 4-[N,N-bis(2-hydroxyethyl)]amino-4’-(2-cinnamoyloxyethyloxycarbonyl)-2’-nitroazobenzene(HACN) with p-phenylenediacyloyl chloride(PD). For the purpose of obtaining an optimized condition of UV irradiation for poling treatment involving photocrosslinking, photoreactivity of these NLO polymer films was investigated. There was observed considerably different photoreaction behavior, especially in photofading of the NLO chromophore, between MACN polymer and HACN-PD polycondensate; the latter faded more rapidly than the former. A reason for this phenomenon was considered.