This study reports on the formation of cadmium sulfide (CdS) nanostructures with controlled morphology synthesized via a simple chemical route in surface active agent environment. The effect of organic surface active agents (surfactants) as sodium dodecyl sulfate (SDS), polyethylene glycol (PEG) and cetyltrimethylammonium bromide (CTAB) on structural, morphological, optical and photoelectrochemical properties of CdS thin films have been studied. Our results reveal that the organic surfactants play key roles in tweaking the surface morphology. A compact spongy ball like morphology was observed for the CdS samples grown without organic surfactants. The cauliflower's with nanopetals from the CTAB, whereas crowded star fish like morphology is observed in PEG-mediated growth. Water hyacinth like morphology is tweaked using SDS. Considering the importance of these nanostructures, the growth mechanism has been discussed in details. Additionally, the samples are photoelectrochemically (PEC) active and having a compact surface with a nanoporous structure twig helps in improved photoelectrochemical performance compared to that of CdS deposits from surfactant free solution. This is a simplistic way to tune the morphology using surfactants, which can be applied to other energy conversion applications. (C) 2014 Elsevier B.V. All rights reserved.