TiO2 get positively charged upon UV-irradiation and repel the cationic pollutants away from the surface. Hybridization of AC onto TiO2 (ACT) tends catalyst surface negatively charged besides providing highly favorable adsorptions sites for cationic pollutants. The photodegradation of benzalkonium chloride (BKC), a quaternary ammonium surfactant and a pharmaceutical, is investigated with ACT. The surface charge of the catalyst in surfactant and non-surfactant aqueous dispersion under UV-irradiation is investigated and explained. The anomalous increase in COD values at the beginning of BKC-photodegradation is explained. The intermediate products formed are identified in both solution and solid phase. Trace amount of dodecane remained adsorbed on the catalyst surface after 1 h UV-irradiation, but complete mineralization of BKC is achieved with 2 h UV-irradiation. We propose that BKC photodegradation starts by central fission of benzyl C-N bond followed by dealkylation, and demethylation steps. (C) 2015 Elsevier B.V. All rights reserved.