© 2022 IOP Publishing Ltd.A novel Al/CrO3/p-Si structure was built by help the spin coating technique. CrO3 thin layer has been characterized by the XRD, UV-vis, SEM and AFM measurements. It has been observed that the CrO3 layer has amorphous structure with optical band energy value of 3.96 eV. The surface analysis of CrO3 layer by using AFM and SEM methods has been found to be rather rough that is not observed grains of any definite shape or size. Furthermore, some electronic quantities of Al/CrO3/p-Si junction by help the thermionic charge transport mechanism have been extracted by utilizing current-voltage (I-V) and capacitance-voltage data. Moreover, it has been seen that interfacial state concentration for the Al/CrO3/p-Si contact varied in the range of 8.05 × 1012 eV−1 cm2 to 6.71 × 1011 eV−1 cm−2 in darkness, and 1.23 × 1013 eV−1 cm−2 to 3.82 × 1012 eV−1 cm−2 under the illumination condition. The photoelectric parameters of the Al/CrO3/p-Si contact under 100 mW cm−2 light illumination was studied by I-V measurement.