One of the challenges facing the fabrication of high-performance conventional structure polymer solar cells (PSCs) is the development of new interface materials that have better air stability and charge carrier collection and transport ability. In this study, the mixture thin films of polyethylenimine ethoxylated (PEIE) and TiOx are developed as the electron extraction layer (EEL) and Ag as the cathode for the application in PSCs, replacing the Ca/Al composite cathode. Ultraviolet photoelectron spectroscopy (UPS) and space-charge-limited current (SCLC) measurements demonstrate that PEIE:TiOx/Ag shows appropriate energy levels, substantially reduced barrier potential, weakened charge carrier recombination and enhanced electron mobility. As a result, the PEIE:TiOx-based PSCs demonstrate not only an enhanced power conversion efficiency (PCE) of 10.94% but also the photovoltaic performance insensitive to the storage time, yielding an aged PCE that is 92% of the fresh PCE. This result can be further explained by the dependence of the charge carrier mobility on storage time. Our work suggests exploiting the PEIE:TiOx/Ag composite thin films as the composite cathode replacing Ca/Al thin films for successfully enhancing the photovoltaic performance and improving the stability of PSCs.