Potentiometry with membrane selective electrodes is preferable for measuring the various constituents of pharmaceuticals. In this work, carbon paste electrodes (CPE) were prepared, modified, and tested for the determination of maprotiline hydrochloride, which acts as an antidepressant. The proposed CPE was based on an ionic association complex of maprotiline-tetraphenylborate, 2-nitrophenyloctyl as a binder, and sodium tetraphenylborate as an ionic lipophilic additive. The optimized composition improved potentiometric properties up to theoretical Nernst response values of −59.5 ± 0.8 mV dec−1, in the concentration range of maprotiline from 1.6 × 10−7 to 1.0 × 10−2 mol L−1, and a detection limit of 1.1 × 10−7 mol L−1. The CPE provides excellent reversibility and reproducibility, exhibits a fast response time, and is applicable over a wide pH range. No significant effect was observed in several interfering species tested. The proposed electrode was used for the precise determination of maprotiline in pure solutions, urine samples, and a real sample—the drug Ludiomil.