Surfactant liquid-membrane type sensors are usually made of a PVC, ionophore and a plasticizer. Plasticizers soften the PVC. Due to their lipophilicity, they influence the ion exchange across the membrane, ionophore solubility, membrane resistance and, consequently, the analytical signal. We used the DMI-TPB as an ionophore, six different plasticizers [2-nitrophenyl-octyl-ether (P1), bis(2-ethylhexyl) phthalate (P2), bis(2-ethylhexyl) sebacate (P3), 2-nitrophenyl phenyl ether (P4), dibutyl phthalate (P5) and dibutyl sebacate (P6)] and a PVC to produce ionic surfactant sensors. Sensor formulation with P1 showed the best potentiometric response to four usually used cationic surfactant, with the lowest LOD, 7 × 10−7 M; and potentiometric titration curves with well-defined and sharp inflexion points. The sensor with P6 showed the lowest analytical performances. Surfactant sensor with P1 was selected for quantification of cationic surfactant in model solutions and commercial samples of disinfectants and antiseptics. It showed high accuracy and precision in all determinations, with recovery from 98.2 to 99.6, and good agreement with the results obtained with surfactant sensor used as a referent one, and a standard two-phase titration method. RDS values were lower than 0.5% for all determinations.