The in situ photochemistry of aqueous colloidal ZnS has been studied in relation to variety of the surfactants as surface passivating agents. The photoluminescence (PL) intensity of ZnS nanoparticles (NPs) has been drastically enhanced as compared to their bare counterparts due to surface passivation by surfactants depending upon their molecular structure. Cationic surfactants of alkyltrimethylammonium bromide series with different chain lengths (C(16), C(14) and C(12)) have been tested. The PL emission of ZnS NPs decreases with decrease in chain length because of ineffective stabilization and passivation of surface because the larger sized NPs were produced in the surfactant with smaller chain length. On the other hand, three anionic surfactants with C(12) chain length with different head groups have been capable of comparatively effective passivation to produce stable NPs with better luminescence. The changing nature of surface states during growth and long time ripening of ZnS NPs has also been monitored by comparing time evolution PL emission in different surfactants. The influence of UV-light irradiation in enhancing the PL emission has been found to be surfactant structure dependent with maximum enhancement observed with the surfactants having pi-electrons in their head group functionalities. The anionic surfactants also display better tendency to retain the enhanced PL of ZnS NPs for longer time durations. (C) 2011 Elsevier B.V. All rights reserved.