Ionic liquids (ILs) have a wide variety of applications in modern electrochemistry due to their unique electrolytic properties. In particular, they are promising candidates as dopants for polymeric membranes in potentiometric sensors and liquid-junction free reference electrodes. However, the effective use of ILs requires a comprehensive understanding of their electrolytic behavior in the polymeric phase. We report here the exploration of the electrolytic and diffusion properties of IL 1-hexyl-3-methyl-1H-imidazol-3-ium bis[(trifluoromethyl)sulfonyl]amide ([C(6)Meim][NTf2]) in a poly(vinyl chloride) matrix. Chronopotentiometry is utilized to determine the concentration of charge carriers, ionic diffusion coefficients and apparent dissociation constant of [C(6)Meim][NTf2] in PVC membranes plasticized with a mixture of [C(6)Meim][NTf2] and bis(2-ethylhexyl) sebacate (DOS) over a wide range of IL concentrations. The diffusion properties of [C(6)Meim][NTf2] are confirmed by NMR-diffusometry. The non-monotonic electrolytic behavior of the IL in PVC-DOS matrix is described for the first time. A maximum ionization degree and diffusion coefficient is observed at 30 wt.% of IL in the plasticizing mixture. Thus, it is shown that by varying the flexible parameter of the IL to plasticizer ratio in the polymeric phase one can tune the electrolytic and transport properties of sensing PVC membranes.