The combination of an emulsion template with polymerization is a very convenient approach to the one-step realization of both simple control porous structures via a change in emulsion formulation and easy functionalization via the concomitant choice of an on-demand monomer. A major challenge of this approach is the inherent instability of the oil/water interface in emulsions, especially the occurrence of chemical reactions in oil or aqueous phases. This study reports the pioneering preparation of highly interconnected macro-mesopores and multicompartment (HIMC) vinyl organosilica microspheres with hydrophobicity by the one-step formation of W/O/W emulsions acting as a :template. The emulsion system consists of acidified deionized water, a stabilizer, and vinyltriethoxysilane (VTEO) in which VTEO can be used to produce an. organosilica skeleton of the resultant microsphere by a sol-gel process. The study demonstrated that the marvelousstability of W/O/W emulsions aids the formation of mtilticompartment organosilica microspheres with highly interconnected macro-mesopores by emulsion droplets rather than single -compartment (SC) microspheres. Menwhile, the internal porous structure and surface morphology of as-prepared organosilica microspheres could be largely toned by a simple variation of the pH value, the volume fraction of the water phase, and -the stabilizer concentration in the initiating multiemuisions. Benefiting from such a well-orchestrated structure and the existence of numerous vinyl groups on the surface; HIMC organosilica microspheres exhibit very high hydrophobicity (with a water contact angle larger than 160), which allows them to stabilize liquid marbles with excellent stability and high mechanical robustness. Because of its strong catalyst, Ag nanopartides within HIMC organosilica microspheres enable Ag/HIMC-vinyl organosilica microsphere-based liquid marbles to be an efficient catalytic rhicroreactor, realizing the complete degradation of MB to leuco methylene blue by NaBH4 in 10 min. The result of this work could provide some guidance for the easy, low-cost, benign preparation of HIMC microspheres having the potential to be excellent supporter of metal nanoparticles or other functionalized compounds for applications in sensing, optoelectronics, and catalysis.