Background: In this study, we reported on developing a susceptible, accurate, simple, and economical electrochemical sensor for gabapentin determination in capsules. Methods: The ITO electrode was modified with a layer of Prussian blue nanoparticles and then used as the working electrode. Gabapentin was extracted from commercial capsules, and a series of concentrations of gabapentin were prepared for studying the efficacy of the proposed sensor. The electrochemical measurements were performed using cyclic voltammetry and square wave voltammetry techniques. Results: The sensitivity and selectivity of the developed electrode toward gabapentin in different interferences, including citric acid, glucose, and urea, were investigated. The modified electrode showed detection and quantification limits of 31.58 and 94.74 nM, respectively, over a dynamic range of concentrations from 100 nM to 3 μM. Conclusion: The proposed sensor displayed a high sensitivity and selectivity for monitoring gabapentin in pharmaceutical drugs without a noticeable interference. Hence, the modified electrodes are great candidates for gabapentin routine analysis.