We characterized optically and electrochemically synthesised pure PMMA and PMMA–TiO2 nanocomposites developed through various proportions of anatase TiO2 (TiO2 (A)) added by chemical polymerization at room temperature. The characterization of the nanocomposite was carried out using FT-IR, UV-Vis, XRD, and FESEM. Cyclic voltammetric studies exhibit good adherent behaviour on the electrode surface at pH 7.0 for PMMA and pH 4.0 for PMMA–TiO2 nanocomposite. It has been observed that PMMA–TiO2 nanocomposite modified GCE has good oxygen reduction ability, and also enhances resistance behaviour.