Nanoparticulate titanium dioxide (nTiO2) is frequently applied, raising concerns about potential side effects on the environment. While various studies have assessed structural effects in aquatic model ecosystems, its impact on ecosystem functions provided by microbial communities (biofilms) is not well understood. This is all the more the case when considering additional stressors, such as UV irradiation — a factor known to amplify nTiO2-induced toxicity. Using pairwise comparisons, we assessed the impact of UV (UV-A = 1.6 W/m2; UV-B = 0.7 W/m2) at 0, 20 or 2000 μg nTiO2/L on two ecosystem functions provided by leaf-associated biofilms: while leaf litter conditioning, important for detritivorous invertebrate nutrition, seems unaffected, microbial leaf decomposition was stimulated (up to 25%) by UV, with effect sizes being higher in the presence of nTiO2. Although stoichiometric and microbial analyses did not allow for uncovering the underlying mechanism, it seems plausible that the combination of a shift in biofilm community composition and activity together with photodegradation as well as the formation of reactive oxygen species triggered changes in leaf litter decomposition. The present study implies that the multiple functions a microbial community performs are not equally sensitive. Consequently, relying on one of the many functions realized by the same microbial community may be misleading for environmental management.