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Summary Transition metal oxides/silicon heterocontact solar cells are the subject of intense research efforts owing to their simpler processing steps and reduced parasitic absorption as compared with the traditional silicon heterostructure counterparts. Recently, molybdenum oxide (MoOx, x < 3) has emerged as an integral transition metal oxide for crystalline silicon (cSi)‐based solar cell based on carrier‐selective contacts (CSCs). In this paper, we physically modelled the CSC‐based cSi solar cell featuring MoOx/intrinsic a‐Si:H/n‐type cSi/intrinsic a‐Si:H/n+‐type a‐Si:H for the first time using Silvaco technology computer‐aided design simulator. To analyse the optical and electrical properties of the proposed solar cell, several technological parameters such as work function and thickness of MoOx contact layer, intrinsic a‐Si:H band gap, interface recombination, series resistance, and temperature coefficient have been evaluated. It has been shown that higher work function of MoOx induces the formation of a favourable Schottky barrier height as well as an inversion at the front interface, stimulating least resistive path for holes. Utilising thinner MoOx layer implies reduced tunnelling of minority charge carriers, thus enabling the device to numerically attain 25.33% efficiency. With an optimised interface recombination velocity and reduced parasitic absorption, the proposed device exhibited higher Voc of 752 mV, Jsc of 38.8 mA/cm2, fill‐factor of 79.0%, and an efficiency of 25.6%, which can be termed as the harbinger for industrial production of next‐generation efficient solar cell technology.