This work proposes an innovative integration of Membrane Distillation (MD) and photo-oxidation for a continuous recovery of water from arsenic (As) contaminated solutions coupled with the oxidation of arsenite (As(III)) into arsenate (As(V)). Polyvinylidene fluoride (PVDF) mixed matrix membranes (MMMs) containing titanium dioxide nanoparticles (TiO2 NPs) as photocatalyst were developed. A systematic study elucidated the effect of TiO2 NPs on membranes’ morphology prepared via non-solvent-induced phase separation (NIPS) using triethyl phosphate (TEP) as a green solvent for PVDF solubilization. Vacuum membrane distillation (VMD) tests carried out by irradiating the MMMs with ultraviolet (UV) radiation demonstrated the possibility of recovering up to 80 % of the water from As-contaminated synthetic and real multi-ions aqueous solutions from Sila Massif (Italy). The distillate was recovered at a rate of 6.9 …