In this work, thermal decomposition of the [Co(NH3)5(H2O)](NO3)3 precursor complex was investigated under solid state conditions. Thermal analysis (TG/DTA) showed that the complexwas easily decomposed into the Co3O4 nanoparticles at low temperature (175 °C) without using any expensive and toxic solvent or a complicated equipment. The obtained product was identified by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX). Optical and magnetic properties of the products were studied by UV-visible spectroscopy and a vibrating sample magnetometer (VSM), respectively. FT-IR, XRD and EDX analyses confirmed the formation of highly pure spinel-type Co3O4 phase with cubic structure. SEM and TEM images showed that the Co3O4 nanoparticles have a sphere-like morphology with an average size of 17.5 nm. The optical absorption spectrum of the Co3O4 nanoparticles showed two band gaps of 2.20 and 3.45 eV, which in turn confirmed the semiconducting properties. The magnetic measurement showed a weak ferromagnetic order at room temperature. Photocatalytic degradation of methylene blue (MB) demonstrated that the as-prepared Co3O4 nanoparticles have good photocatalytic activity under visible-light irradiation.