Utilization of naturally occurring limonene from renewable biomass as a key starting material for the synthesis of valuable chemicals is a promising avenue to reduce both the dependence on nonrenewable fossil fuels and global CO2 emission. Herein, we report a highly active tremella-like ZnCo2O4 catalyst for the selective oxidation of limonene with molecular oxygen under mild reaction conditions. The developed ZnCo2O4 catalyst exhibits an appealing reaction performance with a limonene conversion of 93.5% (reaction rate of 0.0823 mmol gcat-1 h-1) and selectivity of 75.8% for 1,2-limonene oxide (LO), far outperforming the monometallic oxides of ZnO and Co3O4. Detained experimental characterizations and analyses manifest that the substitution of Zn into the Co3O4 framework can facilitate the formation of more unsaturated coordination sites and oxygen vacancies due to the modified chemical environment of Co atoms, inducing a beneficial synergistic intermetallic effect for the limonene oxidation catalysis.