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.