Inappropriate handling of heavy metal-containing wastewater resulting from extensive mining and smelting activities causes serious threats to surrounding environments and human health. The electrokinetic (EK) technology has been extensively applied to remediate heavy metal-contaminated sites because of its great manoeuvrability. The electrochemical polarization effect, however, reduces the electron transfer rate and could badly degrade EK removal efficiency. To this end, the present work proposed a novel graphene oxide-alginate composite hydrogel and applied it to copper removal as electrodes in EK remediation. A series of laboratory tests concerning its physical, mechanical, adsorption, and electrochemical properties were conducted. The graphene oxide (GO) particles provide larger average pore size and pore volume than traditional activated carbon electrodes. The surface functional groups, including hydroxyl, carboxyl, and epoxide groups, promote hydrogen bond formation. The GO particles and the calcium alginate are crosslinked with the hydrogen bonds, improving the mechanical properties of the graphene oxide-alginate composite hydrogel. Furthermore, the functional groups also encourage copper adsorption, and a high GO proportion does not necessarily mean an improvement in copper adsorption. The dynamic mechanism of Cu(II) adsorption onto the graphene oxide-alginate composite hydrogel conforms with the pseudo-second-order kinetic model. Moreover, the absence of oxidative and reductive peaks in the cyclic voltammograms is mainly attributed to the non-faradaic nature of the graphene oxide-alginate composite hydrogel, indicating a reduced electrode polarization effect. The Nyquist plot also approves its low resistance nature. The results were then compared against other electrodes to highlight the relative merits of the proposed graphene oxide-alginate composite hydrogel electrode.