The thermal decomposition and microwave heating of Co3[Co(CN)6]2 leads to formation of nanostructured porous cobalt oxide (Co3O4). Here, we report Co3[Co(CN)6]2 as a novel single source precursor for the synthesis of phase pure Co3O4 particles at 650°C under mixed argon/oxygen atmosphere as evidenced from X-ray diffraction (XRD) patterns. During thermal decomposition, release of gaseous products like CO2, NxOy, (CN)2 facilitate the formation of a highly porous Co3O4 whose morphology and particle size distribution were characterized using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) respectively. Porous Co3O4 shows high discharge capacity of 1131 mA h g-1 with 96% coulombic efficiency against Li/Li+ reference electrode.