Formation of spinel tricobalt tetraoxide (Co3O4) nanostructures through a controlled thermal oxidation process is discussed here. Thin films of high purity cobalt (Co) were deposited on glass/quartz substrates using an electron beam (E-beam) evaporation technique. Thermal oxidation of the as-deposited Co thin films was carried out at various oxidation temperatures (400°C to 600°C) for different durations (5 hours to 15 hours) to grow various oxide nanostructures. Different surface characterizations techniques were used to investigate the structure, chemistry and electronic properties of the as-grown cobalt oxide nanostructures. X-ray diffraction analysis revealed the presence of the CoO phase along with the Co3O4 phases at relatively lower oxidation temperature. However, the Co3O4 phase becomes more predominant for longer oxidation durations at higher oxidation temperatures. Field emission scanning electron microscopy analysis showed a surface morphological transition from nanowalls to nanograins with an increase in the oxidation temperature. The surface electrical conductivity of the oxidized Co films is also increased for higher oxidation temperature and/or duration mainly due to the oxide phase purity and larger particle sizes. Ultraviolet–visible spectroscopy indicated two distinct optical energy bandgaps, which effectively decreased with an increase in the oxidation temperature and duration. Raman spectroscopy identified five different Raman-active modes corresponding to the Co3O4 phase, with the F2g mode dominating at higher temperatures. All these findings provide clear insights into the structural, electrical, chemical and optical properties of cobalt oxide thin films. Moreover, it provides a mechanism on how to grow 2D nanowalls morphology of Co3O4 films which can further be used in energy, sensor or catalytic applications.