Procedures that lead to surface selective modification of preformed poly(vinyl chloride) (PVC) films are detailed. Using X-ray photoelectron spectroscoy (X.p.s.), ultra-violet (u.v.)-visible spectroscopy and attenuated total reflectance infra-red spectroscopy, we followed the changes induced in PVC films by dehydrochlorination with lithiated alpha,omega-diaminopoly(alkene oxide)s. By controlling the temperature of the reaction, we could control the depth and extent of reaction. After about 20-30 min at -78 degrees C, -42 degrees C or 0 degrees C, the depth of the polyunsaturated layer was about 60 Angstrom, 500 Angstrom or 2000 Angstrom (1 Angstrom = 0.1 nm), respectively, as estimated by u.v.-visible analysis. Further modification at that point occurred at a slower rate. X.p.s. analysis of the changes in the Cl-2p and C-1s signals indicated that about 60% of the vinyl chloride subunits had been consumed by the lithiated amide base in Ih at -78 degrees C. Subsequent modifications of the unsaturated surfaces produced by dehydrochlorination are also described. Nucleophilic substitution led to surfaces grafted by poly(alkene oxide)s or poly(ethylene imine)s. Hydroboration-oxidation or hydroboration-grafting led to surfaces containing hydroxy groups or poly(methyl methacrylate) grafts.