To provide orthogonal solvent processable surface modification and improve the device stability of bulk-heterojunction polymer solar cells (PSCs), n-type semiconducting material naphthalene diimide (NDI) was chemically introduced onto the ITO surface as a cathode interlayer (CIL) using 3-bromopropyltrimethoxysilane (BrTMS) as a coupling agent. After modification, the work function of ITO can be decreased from 4.70 to 4.23 eV. The modified ITO cathode was applied in inverted PSCs based on PTB7-Th:PC71BM. With the CIL modification, a champion power conversion efficiency (PCE) of 5.87% was achieved, showing a dramatic improvement compared to that of devices (PCE = 3.58%) without CIL. More importantly, with these chemical bonded interlayers, the stability of inverted PSCs was greatly enhanced. The improved PCE and stability can be attributed to the increased open circuit voltage and the formation of robust chemical bonds in NDI-TMS films, respectively. This study demonstrated that chemical modification of ITO with n-type semiconducting materials provides an avenue for not only solving the solvent orthogonal problem but also improving the device performance in terms of the PCE and the stability.