In this study, we investigated the structural and optical properties of garlic extract-based green-synthesised tricobalt tetroxide nanoparticles. Transmission electron microscopy revealed a particle size range of 8–22 nm for the prepared powder sample. Powder X-ray diffraction data and Rietveld refinement results confirmed the spinel cubic crystal structure of the tricobalt tetroxide nanoparticles, with an average crystallite size of 11.23 nm. This crystal structure corresponds to the Fd3̅m space group and has an average lattice constant of 0.791 nm. The bond lengths of Co3+‒O2- and Co2+‒O2- are measured to be 0.188 nm and 0.190 nm, respectively. The FTIR data provided evidence of the presence of various functional bands, which helped qualitatively determine the purity of the sample. The UV-Vis spectrum estimated two direct energy band gap values (3.7 eV and 2.2 eV) that may be useful for efficient interaction with a wide range of ray spectra to create more electron-hole pairs for various photo-responsive applications, such as dye degradation, solar cells, and optoelectronic components.