In recent years, the use of ion-selective membranes in the sensing and assessment of environmental contaminants has become a critical goal. Using sodium tetraphenylborate (TPB) and phosphotungstic acid (PTA) as ion-pairing agents, two sensitive and selective sensors were manufactured to evaluate the electrochemical response of moxifloxacin hydrochloride (MOX). The optimal electrochemical behavior was attained by fine-tuning all assay parameters. The manufactured membranes’ performance was optimal in a pH range from 1.0 to 5.0 with a linearity between 1 × 10−6 M and 1 × 10−2 M. The MOX–TPB and MOX–PTA membrane electrodes have Nernstian slopes of 59.2 ± 0.60 mV/decade and 58.4 ± 0.50 mV/decade, respectively. The proposed method was used to determine MOX in its pure form as well as real pharmaceutical wastewater effluents. The fabricated electrodes were effectively applied for the sensitive and selective determination of MOX in actual wastewater effluents without the need for any pre-treatment processes.