In view of the methyl orange (MO) dye on everyday applications in the textile, food, leather, paper, printing, and pharmaceuticals industry, in addition to its toxic behaviour on human health, we have developed a biodegradable polylactic acid (PLA)-based cerium dioxide (CeO2)-graphene oxide (GO) composite by means of a sol-gel technique and tested its efficacy. For the study, the PLA polymer obtained is of renewable agriculture waste origin (sugarcane bagasse) and was isolated by means of fermentation of the feedstock followed by the polymerization of lactic acid. The instrumental techniques such as the powdered x-ray diffraction, scanning electron microscopy etc. were employed for the physical characterization of the material. The various parameters such as the kinetics, desorption, regeneration, pH, isotherm theories, and ionic strength were tested towards the adsorption of MO dye onto the surface of GO-PLA-CeO2 composite. The outcome of the study exhibited that the GO-PLA-CeO2 composite revealed promising behaviour for the dye removal, which was allocated to the efficacy of GO, PLA, and CeO2 properties. Also, the adsorption process of GO-PLA-CeO2 is completely dependent on the initial concentration of MO and the adsorption equilibrium fitted well with the Langmuir isotherm. In addition, the electrochemical characterization of the composite was studied by means of CV and impedance measurements. Based on the outcome of the results, it can be said that the GO-PLA-CeO2 composite may be applied as a suitable electrode material along with its efficient adsorption properties for the removal of MO dye from wastewater.