Vanadium pentoxide xerogels were prepared by the hydrolysis of VO(OC3H7)3 by the sol−gel process. The generation of V2O5 was optimized by a combinatorial approach incorporating rapid screening by Raman spectroscopy. The latter revealed crystallites of vanadium oxide. Subsequently poly(p-ethylphenol) (PEP)/V2O5 nanocomposites were prepared by the sol−gel process at the optimized molar ratio of VO(OC3H7)3/H2O/acetone = 1/45/300. Evidence from Raman spectra indicated that the presence of PEP did not interfere in the formation of crystalline V2O5 in the composites. FTIR also exhibited interaction between PEP and V2O5. TEM showed a fibrous V2O5 structure dispersed in the PEP matrix.