A new thiosemicarbazone ligand was immobilized through a Cu(I)-catalyzed click reaction on the surface of glassy carbon (GC) and electrochemically reduced graphene oxide (GC-ERGO) electrodes grafted with phenylethynyl groups. Using the accumulation at open circuit followed by anodic stripping voltammetry, the modified electrodes showed a significant selectivity and sensibility for Hg(II) ions. A detection limit of 7 nM was achieved with the GC modified electrodes. Remarkably, GC-ERGO modified electrodes showed a significantly improved detection limit (0.8 nM), sensitivity, and linear range, which we attribute to an increased number of surface binding sites and better electron transfer properties. Both GC and GC-ERGO modified electrodes proved their applicability for the analysis of real water samples.