Poly(butyl fumarate) (PBF) was successfully synthesized by two-step reaction with diethyl fumarate and 1,4-butanediol as basic raw material. The polymers were characterized by FTIR, 1HNMR, GPC, TG and DSC. The effects of reaction parameters on the yield of PBF were studied. Based on the polymerization mechanisms, the reaction time, temperature and doses of alcohol were investigated to achieve maximum polymer yield. The results suggested that the appropriate molecular weight (Mn=2773) and higher yield (61.94%) of PBF are obtained when the molar ratio of diethyl fumarate and 1,4-butanediol is 1:3, the reaction temperature is 130 ℃ and the reaction time is 8 h. PBF/N-Vinyl-2-pyrrolidone (NVP) composite was prepared by UV-curing and thermo-curing respectively. And the effects of initiator dosage on crosslinking and curing degree of the composite were also investigated. The results showed that crosslinking and curing effect of the composite were better, when the dosage of photoinitiator and thermal initiator were 2.5% phenyl bis(2,4,6-trimethylbenzoyl)-phosphine oxide (BAPO) and 3% benzoyl peroxide (BPO) [0.2% N,N-Dimethyl-p-toluidine (DMT)], respectively.