Following our report on the fabrication of BiOCl x Br 1-x (0≤ x ≤1) alloys, and via careful rational optimization and substantial tuning, we upgraded the previous photocatalytic system by means of a controlled doping with elemental bismuth particles. The latter leads to the formation of well-defined structures characterized by effective separation of electron-hole pairs and more reductive photo-excited electrons. These advanced semiconductors, specifically heterojunctioned doped alloys, were synthesized via simple soft chemical route at room temperature and used for demonstrating the enhanced and complete mineralization of recalcitrant organic contaminants in water such as toluene, benzene, chlorobenzene, xylene, terephthalic acid and benzoquinone. The molecular photocatalytic mechanism of the above degradation processes was thoroughly elucidated.