Conducting polyaniline/Chromiumoxide (PANI/Cr2O3) composites have been synthesized by insitu deposition technique by placing fine graded Cr2O3 in polymerizationmixture of aniline. The composites are characterized by employing X-ray diffractometry (XRD) and Infrared (IR) spectroscopy. It is observed from the XRD studies that Cr2O3 has retained its structure even though it is dispersed in PANI during polymerization reaction. By observation of IR spectra, it is seen that some of the characteristic stretching frequencies are considerably shifted towards higher frequency side. The surface morphology of these composites was studied by Scanning electron microscope (SEM). Highmagnification SEMimage reveals the presence of Cr2O3 particles (cenospheres) in PANI, which are homogeneously distributed through out the composite sample. The dc conductivity was studied in the temperature range from 40-150 0C. It can be seen that the value of conductivity increases up to 30 wt%of Cr2O3 in PANI and then decreases there after. The dimensions of Cr2O3particles in the matrix have greater influence on the conductivity value.