Highly efficient dopant-free silicon solar cell requires effective electron- and hole-selective contacts. We have recently reported a remarkable efficiency of 21.3% for dopant-free silicon solar cells with a low work function and transparent and conductive MgFxOy electron extraction. The transparent conductive oxide (TCO) films and molybdenum oxide (MoOx) front hole contact also play significant roles in the high efficiency of dopant-free solar cells. In this study, zinc-doped indium oxide (IZO), tin-doped indium oxide (ITO), and titanium-doped indium oxide (ITiO) have been deposited via magnetron sputtering at room temperature. The work function and optoelectrical properties of TCO films and energy band bending together with the MoOx layer are investigated. The impact of this band bending on the photoelectrical performances of devices is analyzed in detail as a function of the MoOx/TCO work function mismatch. The optimized IZO film presents the highest work function (5.21 eV) and conductivity (2140 S/cm), resulting in reduced barrier height at the MoOx/TCO interface and enhanced hole-selective transport. The light-soaking treatment is introduced to repair the sputtered damage during the IZO deposition. Finally, an impressive cell efficiency of 21.0%, together with Voc, FF, and Jsc of 712.4 mV, 76.4%, and 38.6 mA/cm2, respectively, shows great potential and provides an effective solution to obtain highly efficient dopant-free silicon solar cells.