The feasibility of the newly synthesized ionic associates L1 and L2 formed by ionic liquid [C4mim][PF6] and cationic dyes (malachite green and methylene blue) has been tested as a novel ionophore for the preparation of anion-selective polymeric membrane electrodes. The electrode exhibits Nernstian response and enhanced potentiometric selectivity towards [PF6](-) compared to many other anions. The influence of some experimental parameters such as membrane composition, nature of plasticizer and amount of additive on the potential response of the [PF6](-) sensor are investigated. Under the optimized conditions, the response slopes of the membrane electrodes towards [PF6](-) are 59.7±0.5 and 58.1±0.5 mV/decade based on ionophore L1 and L2, respectively, in 1.0×10(-5)-1.0×10(-1) or 1.0×10(-6)-1.0×10(-1) mol/L concentration range. Interestingly, the optimized electrodes based on ionophores L1 and L2 also exhibit Nernstian response characteristics (60.3±0.5 and 56.0±0.5 mV/decade) for tetrafluoroborate anion [BF4](-) in a wide concentration range. Thus, the proposed sensor has been used for the determination of [PF6](-) and [BF4](-) in aqueous ionic liquids samples and the solubility of the [PF6](-) and [BF4](-) based ionic liquids in water. The satisfactory results are obtained.