Moderating oxide/metal-support interactions over redox catalysts is effective way to achieve efficient chemical looping CO2 conversion, however, identify the interaction type, control the interaction intensity, and reveal its correlation with CO yield from a molecular perspective remain challenging. In this work, a crystal engineering strategy for tuning strong electronic interaction over Fe2O3/ZrO2 is reported and demonstrated by theoretical calculations, characterization techniques and reactivity evaluations. CO yield shows a positive correlation with the intensity of electronic oxide/metal-support interaction. Compared to Fe2O3/t-ZrO2, Fe2O3/m-ZrO2 performs 1.8, 2.5 and 3 times of reduction rate, oxidation rate and time-averaged STYCO (560 mmol_CO·s^(-1)·kg_Fe2O3^(-1)). This is related to the role of ZrO2 played during redox cycles: (i) m-ZrO2 shows a stronger electronic oxide-support interaction with iron oxide than t-ZrO2, which forms more oxygen vacancies at the interface to enhance H2 adsorption and facilitate the reduction of iron oxide; (ii) a stronger metal-support interaction between m-ZrO2 and iron provides channel oxygen to promote the oxidation of metallic iron; (iii) stronger electronic transfer from m-ZrO2 to Fe2O3 occurs, which is more conductive to the activation of *CO2 on the catalyst surface; (iv) the existence of m-ZrO2 with high electronic interaction intensity decreases the energy barriers during redox reactions. This work opens a new window to develop efficient redox catalysts by regulating the crystalline structure and intensifying the composition interactions for thermochemical energy conversion and chemical looping applications.