This work evaluated the photocatalytic activity of suspended TiO2, and TiO2-coated glass Raschig rings with respect to degradation of estrogens estrone (E1), 17β-estradiol (E2), and 17α-ethinylestradiol (EE2) in aqueous solutions and wastewater effluent samples. Gas chromatography/tandem mass spectrometry (GC-MS/MS) studies were carried out to identify degradation products for EE2. TiO2 suspensions allowed degradation rates higher than 90% for all studied estrogens in 30 min for an artificial (ultraviolet A) UVA-assisted process and aqueous solution. Immobilized TiO2 showed less favorable degradation kinetics, requiring ca. 60 min to achieve almost complete estrogen degradation. Some derivatized degradation products were identified for the first time by GC-MS/MS applying ultraviolet C (UVC) photolysis and TiO2/UVA photocatalysis. A degradation route was suggested for EE2 in UVC photolysis and TiO2/UVA processes. In the degradation of pretreated sewage samples, the immobilized TiO2 was more efficient than free TiO2, allowing ca. 85% removal of E2 and EE2 in 60 min.