Green chemistry seeks to find alternative synthesis routes that are less harsh to living organisms and the environment. In this communication, a microwave-assisted hydrothermal technique and a thermal annealing method were used in the reduction of graphene oxide (GO) to make reduced GO (rGO). Graphite powder was oxidised using the Improved Hummers’ method, exfoliated, and freeze-dried. Thereafter, an aqueous suspension of GO was reduced under microwave (MW) irradiation for 10 min at 600 W with and without the help of a reducing agent (hydrazine hydrate). Thermal annealing reduction was also conducted under a nitrogen atmosphere at 300 °C for 1 h. Prepared samples were analysed using Raman laser spectroscopy, X-ray diffraction (XRD), transmission electron microscopy (TEM), the Brunauer–Emmett–Teller (BET) method, and X-ray photoelectron spectroscopy (XPS). A successful reduction in the GO functional groups between the sheets was established using XRD. In the Raman analysis, the ratio of the intensity of the D and G band (ID/IG) in graphene sheets assisted in assessing the quality of the graphene films. An estimation of the number of structural defects was calculated using the ID/IG ratio. The Raman analysis showed an increase in the ID/IG ratio after both oxidation and reduction processes. The defect densities of both MW-treated samples were comparable while an increased defect density was evident in the thermally annealed sample. TEM micrographs confirmed the sheet-like morphology of the samples. The rGO sheets obtained from the MW-treated method appeared to be smaller when compared to the rGO ones obtained by thermal treatment. It was also evident from XRD analysis that thermal treatment promoted the coalition of graphitic layers, such that the estimated number of layers was larger than that of GO. The elemental analysis showed that the C/O ratio of GO increased from 2 to 7.8 after MW hydrazine reduction.