In this work, a novel structured Cerium (III) 12-tungstophosphoric acid (CePW)/ordered mesoporous carbon (OMC) composite is synthesized. The characterization of the material by the Fourier transform infrared spectroscopy (FTIR), X-ray powder diffraction (XRD). Raman spectroscopy, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical characterization shows that the novel CePW/OMC composite has improved properties based on the combination of CePW and OMC properties. CePW/OMC can be used to modify the glassy carbon (GC) electrode and the CePW/OMC/GC modified electrode shows an enhanced electrocatalytic activity. This property can be applied in the determination of some biomolecules. Especially, the detection and determination of the guanine (G) in the presence of adenine (A) is achieved. The catalytic current of G versus its concentration shows a good linearity with two good linear ranges from 4.0 x 10(-6) to 8.0 x 10(-5) M and from 8.0 x 10(-5) to 1.9 x 10(-3) M (correlation coefficient = 0.999 and 0.996) with a detection limit of 5.7 x 10(-6) M (S/N = 3). The linear range for adenine is 4.0 x 10(-6)-7.0 x 10(-4) M with a detection limit of 7.45 x 10(-8) M. With good stability and reproducibility, the present CePW/OMC/GC modified electrode should be a good model for constructing a novel and promising electrochemical sensing platform for further electrochemical detection of other biomolecules. (C) 2010 Elsevier Ltd. All rights reserved.