Titanium dioxide nanoparticles (nTiO2) are widely used in numerous products, yet their role in the accumulation and transfer of other contaminants in the aquatic food webs is not well understood. The influence of nTiO2 on inorganic (IHg) and monomethyl mercury (MeHg) accumulation in invertebrate Daphnia magna through waterborne and dietary exposure was thus thoroughly investigated. The results showed that nTiO2 led to a substantial decrease of the total mercury body burden (THg) in D. magna in direct waterborne exposure to IHg/MeHg. However, exposure to nTiO2 pre-treated with IHg/MeHg resulted in an increase of the THg body burden in daphnids. The presence of nTiO2 led to a substantial decrease of the THg in D. magna when exposed to IHg/MeHg via algal food. These effects were more pronounced for IHg than that for MeHg due to the higher adsorption capabilities of nTiO2 for IHg. In addition, high concentrations of nTiO2 favored the trophic transfer of IHg/MeHg through feeding on nTiO2 pre-treated with Hg, however lessened it when D. magna were fed on alga pre-treated with IHg/MeHg. Comparable assimilation efficiency (AE), determined as Hg retained in daphnids after depuration, was observed in D. magna when exposed to IHg/MeHg via algal food regardless the absence or presence of 20 mgL−1 nTiO2. By contrast, an increase of the AE of MeHg through feeding on nTiO2 and alga was found in the presence of higher concentration of 200 mgL−1 nTiO2. The present results will help to better understand the role of nTiO2 on bioavailability and trophic transfer of global contaminants, such as mercury, known to bioaccumulate and biomagnify in the aquatic environment.