To probe the mechanisms responsible for pH and dissolved oxygen (DO) affecting the photodegradation of 17α-ethynylestradiol (EE2) in dissolved humic acid (HA) solution, EE2 aqueous solutions with pH values ranging from 3.0 to 11.0 and different DO conditions were irradiated by using a 300 W mercury lamp equipped with 290 nm light cutoff filters. In 5.0 mg L(-1) HA solutions (pH 8.0), EE2 was degraded at a rate of 0.0739 h(-1) which was about 4-fold faster than that in Milli-Q water. The degradation of EE2 was mainly caused by the oxidation of photogenerated reactive species (RS), and the contribution of direct photodegradation to EE2 degradation was always lower than 27%. Both the direct and indirect photodegradation of EE2 were closely dependent on the EE2 initial concentration, pH value and DO concentration. The photodegradation rate of EE2 decreased with increased initial concentration of EE2 due to the limitation of photon flux. With pH and DO increasing, the degradation rate of EE2 increased significantly due to the increase in the yields of excited EE2 and RS. Among the photogenerated RS, HO˙ and (3)HA* were determined to be the key contributors, and their global contribution to EE2 photodegradation was about 50%. Although HA could generate more (1)O2 than HO˙, the contribution of (1)O2 to EE2 degradation was lower than 13% due to its low reactivity towards EE2. This study could enlarge our knowledge on the photochemical behaviors of steroid estrogens in natural sunlit waters.