In this study the vapour phase surface graft polymerization of acrylonitrile (AN) onto poly(ethylene terephthalate) (PET) film was conducted with benzoyl peroxide (BPO) as an initiator. Effects of reaction time and quantity of BPO on the polymerization were investigated. With the prolongation of reaction time, the graft polymerization took place rapidly at first, then slowed down, and leveled off. With the increase of BPO, the graft yield increased, then remained unchanged, and lastly began to decrease. The surface topography structure of the grafted PET film was observed by SEM. Grafted PET film was characterised by FTIR spectra, SEM photographs and contact angle measurement.