Transition metal-based bimetallic MOF (CoMo-ZIF) with two different metal ions (Co/Mo) possess specific synergistic catalytic effect in olefins oxidation, but poor diffusion efficiency and less active areas limit its application. Herein, a novel CoMo-ZIF-based nanocomposite is fabricated via an in-situ solvothermal approach to break down active area or diffusion efficiency barrier of CoMo-ZIF via employing SBA-15 as the matrix and nanosacle polyoxometalate (POM) as external active species. Characterizations reveal that pristine rose-type CoMo-ZIF (∼350 nm diameter) alters to rambutan-like hollow sphere and eventually self-assembles into hierarchical petal-by-petal nanoflakes (ca. 20∼50 nm in thickness) after SBA-15 and POM introduction, respectively. POM@CoMo-ZIF@SBA-15 with super large pore size (10.44 nm) and increased active (Co2+ + Co3+)/satellite (1.92) exhibits excellent catalytic activity in cyclopentene (CPE) oxidation to glutaric acid (GAC) with 57.1 % CCPE, 61.6 % SGAC, and good reusability with 54.3∼57.1 % CCPE and 58.4∼63.2 % SGAC during 6 cycles. What's more, thermodynamic analysis indicates that CPE oxidation to GAC is a spontaneous reaction at 273.15∼373.15 K, and kinetic study shows that the key to develop CPE to GAC is to reduce activation energies of cyclopentene oxide ring-opening to 1,2-cyclopentanediol (73.8298 kJ⋅mol−1) and glutaradehyde (118.4571 kJ⋅mol−1). This study not only pioneers a promising strategy for oriented design of MOF-based materials, but also serves as a valuable reference for the computation of various chemical reactions.