We successfully demonstrate inverted structure small-molecule (SM) solar cells with an efficiency of 7.88% using ZnO and PEIE as an interfacial layer. Modification of ZnO with a cost-effective PEIE thin layer increases the efficiency of the inverted cell as a result of reducing the work function of the cathode and suppressing the trap-assisted recombination. In addition to the high efficiency, the inverted SM solar cells are relatively stable in air compared to conventional cells.