Photolytic circulating-bed biofilm reactor (PCBBR) and internal loop photolytic-biological reactor (ILPBR) were respectively used for degradation of phenol, 2, 4, 6-trichlorophenol (TCP) and sulfamethoxazole (SMX). Experimental results indicated that the rates of phenol, TCP and SMX removal by coupled photolysis with biodegradation (P&B) reached at 0.65, 0.11 and 0.17 mg x (L x min)(-1), which was clearly higher than that by photolysis alone (P), biodegradation alone (B), except phenol removal rate by B,which was similar to the rates by P&B. The COD removal percentages of phenol and TCP were 99.5% and 72.1%, and TOC removal percentage of SMX was 57.3, which all were higher that by P and B. The biofilms under UV irradiation were taken as samples for molecular biological analysis to get the significant results that microbial communities in biofilms took great change compared with that without UV irradiation, but they still kept bioactivity degrading organic pollutants. That is significant results for technological innovation on recalcitrant organic wastewater treatment.