Abstract Transition metal oxides (TMO) are extensively applied as a surface passivation and carrier-selective contact layer through replacing boron/phosphorus doped emitter layers in silicon heterojunction (SHJ) solar cell applications. In this regard, molybdenum oxide (MoO3) has drawn a significant attention as a hole extraction layer owing properties such as wide bandgap (∼3 eV), high work function (>6 eV) and low temperature deposition. Thus, we fabricated SHJ solar cells with a dopant-free MoOx applied at the front surface contact layer. Thermally evaporated MoOx films were exhibited optical characteristics such as high transmittance, high bandgap and low absorption coefficient as compared to a-Si:H(p) and μc-SiOx:H (p) layers. X-ray photoelectron spectroscopy (XPS) analysis confirmed the stoichiometric and oxidation deficiency states of the of the MoOx layers. Whereas, MoOx films undergoing long-term air exposure showed an increase in Mo5+ cations due to the increased oxygen vacancy. The fabricated MoOx/c-Si heterojunction solar cells achieved a significant power conversion efficiency (η) of 20%, best open circuit voltage (Voc) of 695 mV, high short circuit current density (Jsc) of 38.88 mA/cm2 and a fill factor (FF) of 74.0%. These results implying that MoOx is as an excellent dopant-free material for alternate p-doped a-Si:H emitter layers in SHJ solar cell applications.