Developing catalysts for the selective oxidation of alkenes with environment‐friendly, unique structural characteristics, high economic benefit and better catalytic performance is important. Herein, we employed ZIF‐67 as the sacrificial template to synthesize bimetallic‐organic frameworks CoxMo100‐x‐ZIF nanocages by a facile dissolution‐regrowth strategy. The Co51.8Mo48.2‐ZIF catalyst was tested under various experimental parameters for the selective oxidation of cyclooctene to screen the optimal reaction conditions. Under the optimal reaction conditions, Co51.8Mo48.2‐ZIF nanocages exhibited a high cyclooctene conversion of 99.3 % and a selectivity of 99.0 % to epoxy cyclooctane. Furthermore, Co51.8Mo48.2‐ZIF nanocages can maintain their catalytic performance after reused five catalytic cycles. This bimetallic catalyst could also be used for the epoxidation of a wide range of alkenes, such as hexene or cyclohexene. In addition, the kinetic studies were conducted, and a reasonable reaction mechanism was proposed based on density functional theory calculations. The outstanding catalytic performance of CoxMo100‐x‐ZIF nanocages can be attributed to the cooperativity between Co and Mo sites and the hollow structure with high surface areas.