A simple methodology has been demonstrated to synthesize various nanocrystalline Cu2O materials assisted by composite surfactant system, SDS and Tween 80 using the polyol method. Glycolaldehyde prepared in situ by heating ethylene glycol solvent at 160 degrees C for 2 h, was utilized as the reducing agent. The relative ratio of the two surfactants was manipulated to achieve different Cu2O morphologies, e.g. nanocrystalline Cu2O flowers, hollow spheres consisting of holes and ring type structure. The FT-IR spectroscopy confirmed that the SDS and Tween 80 moieties were indeed present on the surface as capping agents in order to stabilize the surface nanocrystallites by the co-ordinative interactions between the oxygen atoms of Tween 80 and SDS and the Cu atoms at the surface of the synthesized Cu2O particles. These oxygen atoms eventually encourage the oxidation of the surface Cu atoms to form a thin CuO layer, presence of which on the surface was corroborated by the XPS measurements. Sputtering of the samples was also carried out to remove the surface CuO thin layer and expose the inner Cu2O. These nanomaterials were then investigated for their potential applications in photocatalytic degradation of Rhodamine B dye. (C) 2011 Elsevier BM. All rights reserved.