The UV-curable telechelic polysulfones with (meth) acrylate functionalities were synthesized by condensation polymerization and subsequent esterification. The final polymers and intermediates at various stages were characterized by (1)H NMR, FT-ATR, and GPC. The oligomeric films prepared from the appropriate solutions containing these telechelics and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as the photoinitiator undergo rapid polymerization upon irradiation forming insoluble networks. The photo-curing behavior was investigated by photo-DSC and the effects of the molecular weight of the polysulfone precursor and type of functionality on the rate of polymerization and conversion were evaluated. Thermal properties of the photochemically cured films were studied by differential scanning calorimeter (DSC) and thermal gravimetric analysis (TGA).