Carbamazepine (CBZ) is a pharmaceutical compound recalcitrant to conventional wastewater treatment plants and widely detected in wastewater bodies. In the present study, advanced oxidation processes for carbamazepine removal are investigated, with particular regard to the degradation pathways of carbamazepine by photoelectrocatalysis and conventional photocatalysis. Photoelectrocatalysis was carried out onto TiO₂ meshes obtained by Plasma Electrolytic Oxidation, a well-known technique in the field of industrial surface treatments, in view of an easy scale-up of the process. By photoelectrocatalysis, 99% of carbamazepine was removed in 55 min while only 65% removal was achieved by photolysis. The investigation of the transformation products (TPs) was carried out by means of UPLC-QTOF/MS/MS. Several new TPs were identified and accordingly reaction pathways were proposed. Above 80 min the transformation products disappear, probably forming organic acids of low-molecular weight as final degradation products. The results demonstrated that photoelectrocatalysis onto TiO₂ meshes obtained by plasma electrolytic oxidation is a useful alternative to common advanced oxidation processes as wastewater tertiary treatment aimed at removing compounds of emerging concern.