Indium tin oxide (ITO)/silicon (on both n- and p-type) junctions are prepared at 380 degrees C by spray pyrolysis technique. The ITO/p-Si yielded an ohmic contact. The photovoltaic behaviour of ITO/n-Si junctions as a function of oxidation time tox is reported in the present paper with the view to understanding the role of the interfacial oxide layer in the photovoltaic process. The junctions have been characterized by I-V and C-V measurements. A maximum efficiency of 9.4% is observed (under GE-ELH illumination of 100 mW cm-2) for both small (0.04 cm2) and large (1.0 cm 2) areas of ITO/n-Si junctions at an oxidation time of 60 s. The junctions are observed to be quite stable with time.