A laser-induced surface graft, polymerization method is reported in which surface radicals generated upon laser irradiation initiated radical polymerization. The radical concentrations generated upon excimer laser irradiation under vacuum on poly(ethylene terephthalate) film surfaces were measured using a radical scavenger, 1,1-diphenyl-2-picrylhydrazyl. The density of surface radicals increased with laser fluence at low fluences but decreased at high fluences. Upon laser irradiation and subsequent treatment with gaseous N,N-dimethylacrylamide, surface graft polymerization occurred.