The development of highly sensitive, long-lasting and cost-effective dual hydrogen peroxide (H2O2)2)/glucose sensors is crucial for various industries, particularly in medical, clinical diagnostics, pharmaceuticals, environmental monitoring and food business. In our study titanium dioxide/copper oxide (TiO2/CuO) hierarchical nanostructure electrodes have been grown using hydrothermal process and their nonenzymatic H2O2 sensing and glucose sensing properties have been demonstrated using cyclic voltammetry and amperometry measurements. The surface morphology of TiO2 nanorods (TiO2 NRs) and TiO2/CuO hierarchical nanostructure was investigated using a scanning electron microscope (SEM). The TiO2/CuO hierarchical nanostructure electrodes demonstrated sensitivity of 20.09 μμA mM−1−1 cm−2−2 toward H2O2, in the concentration range 0.25–18.25 mM. The TiO2/CuO hierarchical nanostructure electrodes demonstrated a sensitivity of 1.5 mA mM−1−1 cm−2−2 towards glucose, in the concentration range 0.05–5 mM. Furthermore, artificial neural networks (ANN) were used to model the observed experimental results.