Using ammonia and Co(CH3COO)2centerdot4H2O as starting materials, a facile and surfactant-free route to controlled synthesis of Co3O4 nanoparticles was proposed. Co3O4 nanoparticles with average sizes of 3.5, 6, 11, 19 and 70 nm were obtained through adjusting the ethanol amount in the solvent (the ratio of ethanol to water) or the concentration of raw materials. In this process, the presence of enough O2 was crucial for the formation of pure Co3O4 phase. The environmental catalytic properties of as-obtained Co3O4 nanoparticles were investigated. The results indicated their remarkable catalysis for ozonation degradation of phenol, which denoted a promising application as catalyst in waste-water treatment.