This paper reports a comparative study of electrochemical oxidation and reduction of lamotrigine (LMT) at a modified glassy carbon electrode (MWCNT/RGO–GCE) and a cyclic renewable silver amalgam film electrode (Hg(Ag)FE). Therefore, square wave voltammetry was employed to enable comparison of electrode mechanisms and analytical responses by analysis of voltammetric signals. The analytical performance of both electrodes, including quantification and detection limits, recovery, and reproducibility, was evaluated. The prepared sensors showed good sensitivity and selectivity for LMT determination in pharmaceutical formulations and urine samples. The results indicated that both of the tested electrodes and the developed methods can be considered as suitable tools and interesting alternatives in terms of analytical determination of lamotrigine. It was also stated that the recorded reduction signal is a consequence of two-electron process involving reduction of the azo group, while the oxidation peak is attributed to grafting and further dimerization of LMT molecules. AFM microscopy was used to characterize the modified electrode structure.