Boron subphthalocyanine (SubPc) has special physical and chemical properties, originating from its non-centrosymmetric, near-planar taper structure and large conjugated system; it can act as an alternative to the small molecule hole-transporting material 2,2’,7,7’-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluorene in perovskite solar cells. To achieve a higher solubility in common organic solvents and a more suitable highest occupied molecular orbital (HOMO) energy level that aligns with the valence band of the perovskite material, a SubPc molecule with a hexamethyl substitution at its peripheral position (Me6-SubPc) was successfully designed and synthesized in a one-step method. Completely solution processed perovskite solar cells were fabricated with only a small hysteresis, a power conversion efficiency (PCE) of 6.96% and Voc of 0.986 V.