摘要： Most of the high performance in perovskite solar cells (PSCs) have only been achieved with two organic hole transporting materials: 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9-spirobifluorene (Spiro-OMeTAD) and poly(triarylamine) (PTAA), but their high cost and low stability caused by the hygroscopic dopant greatly hinder the commercialization of PSCs. One effective alternative to address this problem is to utilize inexpensive inorganic hole transporting layer (i-HTL), but obtaining high efficiency via i-HTLs has remained a challenge. Herein, a well-designed inorganic–organic double HTL is constructed by introducing an ultrathin polymer layer dithiophene-benzene (DTB) between CuSCN and Au contact. This strategy not only enhances the hole extraction efficiency through the formation of cascaded energy levels, but also prevents the degradation of CuSCN caused by the reaction between CuSCN and Au electrode. Furthermore, the CuSCN layer also promotes the formation of a pinhole-free and compact DTB over layer in the CuSCN/DTB structure. Consequently, the PSCs fabricated with this CuSCN/DTB layer achieves the power conversion efficiency of 22.0% (certified: 21.7%), which is among the top efficiencies for PSCs based on dopant-free HTLs. Moreover, the fabricated PSCs exhibit high light stability under more than 1000 h of light illumination and excellent environmental stability at high temperature (85 °C) or high relative humidity (>60% RH).