Abstract Rare earth ions possess highly conductive, magnetic, electrochemical and luminescent properties, multiple valence electrons and long lifetime of excited state, thus could be alternatives as dopant to tune and promote the cathode interlayer property in solar cells. In this work, we study the modification of cathode interlayer by rare earth ion doping, based on the model of Yb doped ZnO by sol-gel method. A relative low doping concentration (below 1%) can improve the electron transport of ZnO and the solar cell performance. This is also confirmed by the obtained photocurrent density, excitons generation rate and electron mobility of device. The best PCE 11.04% (with VOC 0.940 V, JSC 16.58 mW cm−2, FF 70.7%) is achieved with 0.5% Yb doping, based on PBDB-T:IT-M active layer, compared to the reference PCE of 10.19% with pure ZnO ETL. While with concentration over 1%, the Yb doping decreases the device performance.