Utilization of systems that can bypass costly materials and methods and have long-term stability is critical for the commercialization of perovskite solar cells (PSCs). Since hole transport materials (HTM) are the major costly layers in PSCs, finding a suitable replacement would be advantageous. Two types of mesoporous PSCs were fabricated using the solution-processed Cr2O3 in pure and composite form with multi-walled carbon nanotube (MWCNT/Cr2O3) as dopant-free, hydrophobic HTM layers. Incorporation of the Cr2O3 into MWCNT rendered improved morphological characteristics and better energy level alignment, facilitating the extraction of holes. Furthermore, such a modification suppresses the hysteresis and interfacial recombination of charges, resulting in a device with long-term stability and the PCE boosted from 12.22 % (bare Cr2O3) to 16.29 % (MWCNT/Cr2O3 nanocomposite). The reason for the increased efficiency of the composite layer than bare Cr2O3 is the decrease of interfacial recombination of charges proved by various electrochemical analysis. The lifetime and processes of transfer and recombination of charges in the interfacial contact as well as hole mobility were explored through various electrochemical techniques. As a result, this work not only demonstrates the potential application of MWCNT/Cr2O3 as an HTM layer for realizing efficient PSC, but also provides a fundamental insight for achieving cost-effective photovoltaic devices with acceptable efficiencies and remarkable stability with just a 0.32 % drop of PCE after 50 days in relative humidity ∼ 40 % under one-sun illumination.