Due to the frequent detection of sulfonamides and quinolones in surface water, trimethoprim (TMP) and enrofloxacin (EFX) were selected as target compounds to compare the degradation efficiency and kinetics of TMP and RFX in UV, UV/peroxymonosulfate (UV/PMS), UV/persulfate (UV/PDS), and UV/hydrogen peroxide (UV/H₂O₂) under different water matrix backgrounds. The quantum yields of TMP and EFX photodegradation were calculated at different pH values. Results show that the pseudo first-order rate constant k₀ of TMP and EFX increased with the increase in pH, and the k₀ of EFX photodegradation was significantly greater than that of TMP. At pH 3.0,7.0, and 11.0, the quantum yields of TMP and EFX photodegradation (λ=254 nm) were calculated as 0.001 0,0.001 3,0.003 6, and 0.005 3,0.051 1,0.064 5, respectively. The coupling of peroxides with UV increased the degradation rate of TMP and EFX, and an obvious enhancement was observed for TMP degradation, which had a small k₀ of photodegradation. Under the background of ultrapure water, the k₀ of TMP and EFX degradation by UV/PDS was the largest at pH 3.0 and 7.0, while the k₀ of UV/PMS system was the largest at pH 11.0. In tap water, the degradation rates of TMP by UV/PMS and UV/PDS were close, which were greater than that of UV/H₂O₂ system, while for EFX degradation, the degradation efficiency of UV/PDS was the largest. In surface water, the efficiencies of TMP degradation by the three systems were close, among which UV/H₂O₂ was the best, while the degradation rate of UV/PDS for EFX was the highest.