Over the last ten years, there has been a remarkable enhancement in the power conversion efficiency (PCE) of perovskite solar cells (PSCs), with poly (3,4-ethylenedioxythiohene):poly (styrenesulfonate) (PEDOT:PSS) emerging as a prevalent choice for the hole transport layer (HTL). Nevertheless, the evolution of the widely utilized PEDOT:PSS HTL has not kept pace with the swift advancements in PSC technology, attributed to its suboptimal electrical conductivity, acidic nature, and inadequate electron-blocking performance. This study presents a novel approach to enhance the HTL by introducing molybdenum oxide (MoO3) into the PEDOT:PSS, leveraging the conductivity and solution processing compatibility of MoO3. Two methods for MoO3 integration were explored: an ammonium molybdate tetrahydrate (AMT) precursor and the direct addition of MoO3 nanoparticles. The carrier dynamics of PSCs modified by MoO3 are significantly optimized. Therefore, the PCE of the device modified by AMT and molybdenum oxide is increased to 18.23 and 19.64%, respectively, and the stability of the device is also improved. This study emphasizes the potential of MoO3 in contributing to the development of more efficient and stable PSCs.