Mesoporous CdS spheres with large surface areas and ordered pore size distribution were synthesized through a facile solution processes. Their potential application in integrated hybrid (poly[2-methoxy-5-(20-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV)/CdS) photovoltaic cells has been demonstrated. The MEH-PPV-CdSMS electrode shows improved photoelectrochemical properties with the maximum conversion efficiency (Elf) of 2.39% with a short circuit current (J(SC)) of -4.26 mA/cm(2), an open-circuit voltage (V-oc) of 0.824 V. and a fill factor (FF) of 68.6%. The good performance, low cost and straightforward fabrication method made the mesoporous CdS materials promising for the development of effective photoelectrochemical cells and a powerful tool for a wide range of applications in modern photoelectronics. (C) 2011 Elsevier Ltd. All rights reserved.