Surface modification of a hydrophobic acrylic polymer film has been performed through simple chemical treatment to give a reactive surface. 2-Triphenylstannylthioethyl acrylate was polymerized under UV-illumination with various contents of a comonomer. When the polymer film was treated with fluoride ion, thiol functional group (SH) was generated on the film surface, which was observed through infrared absorption spectroscopy. The surface was functionalized by thiol addition reaction to acrylic chromophores. The SH content on the surface was controlled with a comonomer, tris(hydroxymethyl)ethane triacrylate, and examined with UV-Vis absorbance of the chromophore attached film. Similarly, a polymer film from 2-tributylstannylthioethyl acrylate was prepared. Destannylation from the triphenylstannyl and tributylstannyl surface completed after 30 and 5 min, respectively. The SH-exposed surface was modified with an isocyanate attached chromophore within 10 min, while acrylic chromophore required 24 h.