Poly(9-vinylcarbazole) (PVK) is an attractive hole transport layer (HTL) for high efficiency perovskite solar cells (PSCs). But there is still some room for improvement in energy level alignment between the highest occupied molecular orbital (HOMO) of PVK and the perovskite layer. In this work, the solvent of PVK-based HTL was optimized to adjust the energy level of HTLs by changing the volume ratio of chlorobenzene (CB) in dimethylformamide (DMF). Experimental results shows that 20% is the optimal ratio of CB in DMF, based on which the HOMO level of HTL was lifted from −5.62 eV to −5.44 eV. Meanwhile, the morphology of perovskite layer with larger grain size and lower trap density was obtained. As a result, the V_OC and J_SC of PSCs was enhanced, leading to the increase of PCE from 15.41% to 18.27%. This work paves the way to realize high-efficiency PSCs based on PVK HTL.