Selecting 17α-ethynylestradiol (EE2) as the target pollutant and TiHAP as the catalyst, comparative studies of the photocatalytic degradation of TiHAP and TiO₂ were conducted, and the influencing factors and intermediate products were also investigated. The results show that the EE2 degradation rate by TiHAP film was faster than that by TiO₂ film. The EE2 degradation rate of TiHAP remained the same with the increase of Fe³⁺ concentration, but decreased with the increase of FA concentration. For TiO₂, the EE2 degradation rate initially increased and then decreased with increasing Fe³⁺ concentration, and increased with increasing FA concentration. The photocatalitic degradation intermediates of EE2 by TiHAP were identified by LC-MSⁿ. The results show that nine kinds of intermediates were identified. Compared with TiO₂, more kinds of intermediates were identified for EE2 photocatalytic degradation by TiHAP. Transformation of the phenolic moiety, hydroxylation, ring opening and carboxylation, and carboxylation were the primary reaction pathways.