The occurrence of micropollutants (MPs) in the aquatic environment poses a threat for the environment and the human health. The application of advanced oxidation processes based in sulphate radicals (SR-AOPs) to eliminate these contaminants has attracted attention in recent years. In this work, the simultaneous degradation of 20 multi-class MPs (classified into 5 main categories, namely antibiotics, beta-blockers, other pharmaceuticals, pesticides, and herbicides) was evaluated for the first time in secondary treated wastewater, by activating peroxymonosulfate (PMS) by UV-A radiation, without any pH adjustment or iron addition. The optimal PMS concentration to remove the spiked target MPs (100 μg L -1 ) from wastewater was 0.1 mM, leading to an average degradation of 80% after 60 min, with most of the elimination occurring during the first 5 min. Synergies between radiation and the oxidant were demonstrated and quantified, with an average extent of synergy of 69.1%. The optimized treatment was then tested using non-spiked wastewater, in which 12 out of the 20 target contaminants were detected. Among these, 7 were degraded at some extent, varying from 10.7% (acetamiprid) to 94.4% (ofloxacin), the lower removals being attributed to the quite inferior ratio of MPs to natural organic matter. Phytotoxicity tests carried out with the wastewater before and after photo-activated PMS oxidation revealed a decrease in the toxicity and that the plants were able to grow in the presence of the treated water.Therefore, despite the low degradation rates obtained for some MPs, the treatment effectively reduces the toxicity of the matrix, making the water safer for reuse.