This study investigated the TiO2 photocatalytic degradation and transformation of the oxazaphosphorines ifosfamide (IFO), cyclophosphamide (CP) and trofosfamide (TRO). Under the optimum conditions of TiO2 = 100 mg/L, IFO = 100 mu g/L and solution pH = 5.5, IFO was completely removed within 10 min (k = 0.433 min(-1)). The results indicated that (OHfree)-O-center dot radicals generated by valence holes in the bulk solution were the predominant species for the degradation of IFO. At higher initial concentrations of oxazaphosphorines (20 mg/L), >50% of TOC remained after 6 h of reaction time, indicating that parent compounds were transformed to byproducts, which exhibit higher Microtox acute toxicities; chlorinated byproducts were likely the source of toxicity. Photocatalytic degradation pathways of the three oxazaphosphorines were proposed. IFO, CP and TRO follow very similar pathways and bond-breaking processes: ketonization and breaking of the C-CI bond, the P-N bond and the C-N bond (N-dechloroethylation). Chloride (Cl-) release is likely the first and primary step in the decomposition process. Several of the identified byproducts were also metabolites, which implies that photocatalytic oxidation proceeds through pathways that are similar to metabolic pathways. (C) 2015 Elsevier B.V. All rights reserved.