Immobilized and visible-light-active titanium dioxide (TiO2) is widely used for water treatment. However, the accelerated generation of degradation byproducts is a potential risk of TiO2-based photocatalysis. This study aimed to investigate the structural effect of engineered TiO2 samples on the formation of major nitrosamines during photocatalysis. The nitrogen-containing impurities and leached metal ions from doped-TiO2 samples could exacerbate nitrosamine formation potential (FP) in distilled water, secondary effluent, and chloraminated water. Doped-TiO2 with 2-ethylimidazole, trimethylamine, triethylamine, and N-carbon nanotubes could leach in the range of 47–64 ng L−1 nitrosamines (including N-nitrosomethylethylamine, N-nitrosodiethylamine, N-nitrosodimethylamine, and N-nitrosopyrrolidine) even under dark conditions. Furthermore, we investigated the role of metal dopants on nitrosamine-FP during the chloramination of precursors such as dimethylamine and microcystin-LR. Metal ions such as Cu that leached from the metal-doped catalysts may catalyze the nitrosamine-FP. Therefore, pre-purification (washing) and immobilization of doped-TiO2 samples on substrates are suggested to remove a considerable amount of nitrosamines. However, during the prolonged tryout, the selection of substrates was critical. Polymeric supports, such as polyimide and polyvinylpyrrolidone, can produce up to 85 ng L−1 nitrosamine, whereas TiO2 immobilized onto steel mesh can remove nitrosamine formation during photocatalytic oxidation followed by chloramination. This study systematically screened a diverse range of dopants, supports, and solvents in engineered TiO2 photocatalysts, in 61 samples, and provided novel insights into their effect on nitrosamine formation.​