This study investigated the degradation of five trace organic contaminants (TrOCs) by integrated direct contact membrane distillation (DCMD) and UV photolysis. Specifically, the influence of inorganic ions including halide, nitrate, and carbonate on the performance of the DCMD–UV process was evaluated. TrOC degradation improved in the presence of different concentrations (1–100 mM) of fluoride ion and chloride ion (1 mM). With a few exceptions, a major negative impact of iodide ion was observed on the removal of the investigated TrOCs. Of particular interest, nitrate ion significantly improved TrOC degradation, while bicarbonate ion exerted variable influence—from promoting to inhibiting impact—on TrOC degradation. The performance of DCMD–UV photolysis was also studied for TrOC degradation in the presence of natural organic matter, humic acid. Results indicated that at a concentration of 1 mg/L, humic acid improved the degradation of the phenolic contaminants (bisphenol A and oxybenzone) while it inhibited the degradation of the non-phenolic contaminants (sulfamethoxazole, carbamazepine, and diclofenac). Overall, our study reports the varying impact of different inorganic and organic ions present in natural water on the degradation of TrOCs by integrated DCMD–UV photolysis: the nature and extent of the impact of the ions depend on the type of TrOCs and the concentration of the interfering ions.