A novel structure denoted as a “multiroom carbon hybrid”, which comprises empty voids dispersed in metal oxide-, sulfide-, and selenide-carbon composites is introduced. Multiroom-structured carbon hybrid microspheres of single component Co3O4 and NiO and multicomponent (Ni0.5Co0.5)Ox were successfully prepared using a one-pot spray pyrolysis process. Liquid-liquid phase segregation during the spray pyrolysis process is a key requirement for generating multiroom-structured metal oxide-carbon hybrid microspheres. Multiroom-structured CoSe2-graphitic carbon (GC) and CoS2-CoS-GC hybrid microspheres were also prepared using a simple post-treatment process. Multiroom-structured CoSe2-GC hybrid microspheres have superior sodium-ion storage properties to bare CoSe2 microspheres. The reversible discharge capacities of the CoSe2-GC and CoS2-CoS-GC hybrid microspheres for the 100th cycles at a current density of 0.2Ag−1 are 393 and 334mAhg−1, respectively. The discharge capacity of the multiroom-structured Co3O4-C hybrid microspheres for lithium-ion storage at a high current density of 3Ag−1 for the 150th cycle is 1243mAhg−1.