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The UV, UV/VUV photolysis and their combination with persulfate (S₂O₈²⁻) were studied for the elimination of trimethoprim and 5-fluorouracil. Methods were examined in terms of transformation and mineralization rate and the matrix effect. The relative contribution of the direct UV photolysis and radical-based reactions (^•OH, SO₄^•⁻) were also investigated. Without S₂O₈²⁻, the efficiency of UV/VUV photolysis highly exceeds that of UV photolysis due to the ^•OH formation, while in the presence of S₂O₈²⁻, the dominant reaction partner is SO₄^•⁻. However, SO₄^•⁻-based methods proved to be efficient for both transformation and mineralization; they are sensitive for the matrix components.