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In this study, we investigated the influence of pH on the hydrothermal synthesis of copper (II) oxide <i>CuO</i> nanostructures with the aim of tuning their morphology. By varying the pH of the reaction medium, we successfully produced <i>CuO</i> nanostructures with three distinct morphologies including nanoparticles, nanorods, and nanosheets according to the pH levels of 4, 7, and 12, respectively. The observed variations in surface morphology are attributed to fluctuations in growth rates across different crystal facets, which are influenced by the presence of intermediate species within the reaction. This report also compared the structural and optical properties of the synthesized <i>CuO</i> nanostructures and explored their potential for photoelectrochemical glucose sensing. Notably, <i>CuO</i> nanoparticles and nanorods displayed exceptional performance with calculated limits of detection of 0.69 nM and 0.61 nM, respectively. Both of these morphologies exhibited a linear response to glucose within their corresponding concentration ranges (3–20 nM and 20–150 nM). As a result, <i>CuO</i> nanorods appear to be a more favorable photoelectrochemical sensing method because of the large surface area as well as the lowest solution resistance in electroimpedance analysis compared to <i>CuO</i> nanoparticles and nanosheets forms. These findings strongly suggest the promising application of hydrothermal-synthesized <i>CuO</i> nanostructures for ultrasensitive photoelectrochemical glucose biosensors.