A new class of two-dimensional (2D) metal carbides, nitrides, and carbonitrides called MXenes has gathered more interest due to their photovoltaic applications. For the MXenes, different surface termination techniques grant them various roles to improve the perovskite solar cell (PSC) performance. Based on the experimental evidence, the bandgap of the active layers in the PSC was not altered; however, their work function was greatly influenced. We report the influence of additive Ti 3 C 2 T x MXene into the absorber and electron transport layers in a PSC, and how it is beneficial to boost the PSC performance using the Solar Cell Capacitance Simulator (SCAPS) simulation tool. The considered architecture contains the methylammonium lead triiodide (MAPbI 3 ) absorber layer, TiO 2 electron transport layer, and CuSCN hole transport layer (HTL). The first-principles density functional theory (DFT) calculations were utilized to get the optical and electrical properties of the β-CuSCN HTL. An optimization procedure was taken to improve the power conversion efficiency (PCE). An overall conversion efficiency of 22.73% can be achieved with MXene assisted structure which is mainly due to a reduction in conduction and valence band offsets that have occurred through the adjustment of electron affinity in the absorber and electron transport layers.