A novel and facile strategy to realize selective inorganic ligand (S2-) exchange on Pb-rich surface of PbS colloidal quantum dots (QDs) has been demonstrated. This was achieved via xanthate ligand decomposition at room temperature without damaging the QDs surface. This proposed method offers an amicable solution for the limitation that inorganic-terminated colloidal QDs are restricted by the specific requirement to solvents with high dielectric constant. Furthermore, Introduction of S2- to form sulfur-crosslinking PbS QDs enables reaction force-induced QDs arrays and smooth surface morphology of the spin-coated QDs film as evidenced by atomic force microscopy. Passivation of QDs by bromide combined with sulfur led to stronger electronic coupling between adjacent QDs as compared to bromide-only passivated QDs counterparts. Bromide and sulfur hybrid-capped QDs exhibited remarkably enhanced carrier mobility from 1.66 x 10(-4) cm(2)/V s to 5.0 x 10(-1) cm(2)/V s as evidenced by the Hall- Effect measurement. The smooth QDs film morphology and higher charge transport contributed to the boost in the power conversion efficiency of QDs solar cells up 4.96% compared that using only CTAB passivated PbS QDs solar cells (3.04%). This controlled sulfurization approach paves a potential way for improved optoelectronic properties and devices based on QDs.