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In this work, we investigate the properties of manganese dioxide (MnO 2 ) and graphene oxide (GO) to develop a new photoelectrochemical (PEC) sensor-based MnO 2 -GO heterojunction on stainless steel electrode for chemical detection of copper (Cu(II)) cation. During the PEC detection process and using chronoamperometry, the photocurrent density increases gradually with the addition of incremental Cu 2+ concentration, achieving a relatively low detection limit (0.9120 µM) and a linear interval range from 0.01 to 110 µM with high selectivity and stability under neutral aqueous solution (pH 7.00). In addition, the PEC change of electrode state in presence of Cu(II) cation requires the oxidized state of MnO 2 -GO heterojunction; this can be reached by applying anodic potential to the electrode (E = + 0.8 V). Thus, a switchable, low-cost, regenerative, and sensitive PEC sensor based on the change of MnO 2 -GO heterojunction surface state permits the selective detection of copper.