The degradation of carbendazim (CBZ) through TiO2 photocatalysis, in the presence of halide ions and under near-UV light irradiation, was investigated. HPLC–MS technique was used to characterize the photoproducts. Spectrophotometric analysis showed that CBZ degraded slowly in TiO2 aqueous dispersions containing no salt (CBZ conversion of 6% after ca. 5 h of irradiation). The photodegradation efficiency increased particularly by addition of bromide salts. Indeed, CBZ reached complete degradation after ca. 30 min at the maximum concentration of NaBr used (0.05 M). Two significant aspects have emerged from the data analysis: the bromide role is to cause inhibition of the electron–hole recombination, a reaction known to be competitive with the reactive process; CBZ photodegradation is especially initiated by direct hole transfer pathway, whereas the OH• role is crucial in the catalyst regeneration process. Degradation attempts under sunlight appeared promising for a more sustainable photocatalytic process.