New azidobenzenesulfonamides are synthesized. Their photophysical and photochemical properties have been investigated. The photophysical properties of these compounds were investigated by (1)H NMR, IR, and UV spectroscopy. The surface photomodification of polyethylene (PE) films by using new azidobenzenesulfonamides is carried out. The wetting angles for three liquids of different polarities (water, formamide, and diiodomethane) have been. studied to estimate the surface modification performed. The obtained wetting angles are used for the determination of the surface free energy gamma(S) (gamma), as well as its polar gamma(p)(s), dispersive Owens-Wendt gamma(d)(s), Lifshits-van der Waals gamma(LW) and acid-base gamma(AB) components, by applying the Lifshits-van der Waals/acid-base methods.