Succinic anhydride groups have been introduced on the surface of and in bulk poly(ethylene) film by a mild photochemical process. These groups on the poly(ethylene) film undergo facile transformation to various functional groups such as acids, esters, or amides by reaction with water, amine compounds, or PEG, etc. The surface functionality has been quantitatively estimated by using gravimetry, ATR-FTIR, XPS, and UV-visible spectroscopy. Surface hydrophilicity was characterized by contact angle goniometry. The poly(ethylene) bound to the azobenzene group, exhibiting interesting responses to external stimuli such as photoinduced and thermally induced E:Z isomerization.