Carbon perovskite solar cells (C-PSCs) represent a promising photovoltaic (PV) technology that addresses the long-term operating stability needed to compete with commercial Si solar cells. However, the poor interface contacts between the carbon electrode and the perovskite result in a gap between C-PSC′s performances and state-of-the-art PSCs based on metallic back electrodes. In this work, Cu (II) phthalocyanine (CuPc) was rediscovered as an effective hole-transporting material (HTM) to be coupled with carbon electrodes. In particular, based on computational studies and VASP calculations, it is found that the tetragonal structure of CuPc could efficiently coordinated to perovskite (P) layer via N and Cu atoms to Pb and I atoms, respectively. By systematically optimizing the concentration of the CuPc HTL solution, and screening the coupling of CuPc HTL with two types of carbon electrodes, based on carbon black:graphite (C-G) mixture and reduced graphene oxide (RGO), respectively, a maximum power conversion efficiency (PCE) of 21.4 % (the mean PCE value of 18.57 %) has been achieved. In addition, our cells exhibit satisfactory stability under thermal aging at 85°C, showing less than 20% PCE loss after more than 200 hours. Furthermore, they maintain excellent shelf-life stability, with only 1.3% PCE loss over 20 days under ambient conditions (ISOS-D1). These findings represent a significant step forward in developing commercially competitive C-PSCs, as they combine both high PCE and stability.