We present the spectroscopic and structural characterization of poly-o-methoxyaniline and poly-o-methylaniline intercalated into oxovanadium phosphate. The influence of synthesis conditions was also investigated. Furthermore, for comparison purpose intercalation reactions between polyaniline (PANI) and the matrix also have been performed. Infrared spectra (infrared bands near 1610 and 1500 cm(-1) characteristic of C-C stretching from quinoid and benzenic rings, respectively) suggest that the organic polymers are present in an intermediate oxidation state of emeraldine, which are in agreement with UV-Vis spectra. Under soft reaction conditions (room temperature), only aniline undergoes intercalation reaction, whereas o-methoxyaniline and o-methylaniline react under refluxing by exfoliation-reconstruction process. These different synthetic procedures (topotactic mechanism and exfoliation-reconstruction) result materials with different arrangements of polymeric species into the interlayer space. (C) 2004 Elsevier Ltd. All rights reserved.