The device performance of inverted organic metallohalide perovskite solar cells (OMPSCs) is optimized via tailoring the electrode surfaces with electron- and hole-transporting materials. This work demonstrates the fabrication of PEDOT:PSS-free OMPSCs using a hole-transporting composite material consisting of bilayered vanadium oxide (VO ) and a thermally cross-linked triarylamine-based material X-DVTPD, which contributes to higher V and J values. The hydrophobicity of X-DVTPD resulted in the formation of large perovskite crystals and enhanced the stability of OMPSCs. Integration of ionic fullerene derivative, fulleropyrrolidinium iodide, in OMPSCs as a hole-blocking interfacial layer at the interface with Ag proves effective to further boost the device efficiency to 18.08%.