A liquid membrane nonionic surfactant sensitive electrode has been prepared, based on a new barium pseudocationic complex of a highly ethoxylated fatty alcohol polyglycol ether and tetraphenylborate as sensing material. The complex has been incorporated into the plasticized PVC-membrane and used as sensing material. The electrode exhibited positive linear non-Nernstian response toward different nonionic surfactants and sub-Nernstian response toward tetraphenylborate with the lower detection limit of 3.3 × 10 −7 mol dm −3 in barium chloride solution. The interfering effect of some alkaline, alkaline earth, and heavy metal cations, has been demonstrated by displaying their calibration curves compared with that of Triton X-100. The electrode has been used as an end-point indicator for potentiometric titration of analytical and technical grade polyethoxylated nonionic surfactants, modelled detergent products, and commercial detergents.