Abstract Interfacial disorder is a general method to change the metal-oxygen compatibility and carrier density of heterostructure materials for ionic transport modulation. Herein, to enable high proton conduction, a semiconductor heterostructure based on spinel ZnFe 2 O 4 (ZFO) and fluorite CeO 2 is developed and investigated in terms of structural characterization, first principle calculation, and electrochemical performance. Particular attentions are paid to the interfacial disordering and heterojunction effects of the material. Results show that the heterostructure induces a disordered oxygen region at the hetero-interface of ZFO-CeO 2 by dislocating oxygen atoms, leading to fast proton transport. As a result, the ZFO-CeO 2 exhibits a high proton conductivity of 0.21 S/cm and promising fuel cell power output of 1070 mW/cm 2 at 510 ℃. Based upon these findings, a new mechanism is proposed to interpret the diffusion and acceleration of protons in ZFO-CeO 2 . Our study provides a new strategy to customize semiconductor heterostructure to enable fast proton conduction.