In this work, simple, reliable, eco‐friendly, and quantitative electrochemical sensors were developed to detect chlorhexidine Digluconate (CHX) in a variety of dosage forms, including mouthwashes and intimate douches, as well as chlorhexidine in spiked human saliva. Without any sample pre‐treatment or extraction processes, CHX was measured in colored aqueous formulations. Based on carbon screen‐printed electrodes, two potentiometric sensors (sensors I and II), utilizing graphene nanocomposites (Gr‐NC), were designed (SPEs). An ionophore, 2‐hydroxypropyl‐β‐cyclodextrin, was doped into the Poly Vinyl Chloride (PVC) polymeric membrane to improve sensor selectivity.