In order to combine the properties of inorganic ion exchanger and conducting organic polymer, a new class of organic–inorganic composite cation exchanger PANI–Ti(IV) phosphosulphosalicylate (PTPSS) was synthesized by intercalating polyaniline (PANI) into Ti(IV) phosphosulphosalicylate (Ti(IV) PSS) using sol–gel chemical route with enhanced properties. PTPSS has been characterized by using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy dispersive X-ray (EDAX), thermo gravimetric analysis (TGA-DTG), and Transmission Electron Microscopy (TEM). Ac electrical conductivity studies were also performed. This material possessed electrical conductivity of ${10}^{-3}$ – ${10}^{-6}$${\text{Scm}}^{-1}$which falls in the semiconducting range. The frequency (2 × 10⁵ – 1 × 10⁶ Hz) dependent Ac conductivity at room temperature suggests the evidence for the transport mechanism for the conductivity in PTPSS. The structure of the composite cation exchanger extremely supports its conducting behavior.In order to combine the properties of inorganic ion exchanger and conducting organic polymer, a new class of organic–inorganic composite cation exchanger PANI–Ti(IV) phosphosulphosalicylate (PTPSS) was synthesized by intercalating polyaniline (PANI) into Ti(IV) phosphosulphosalicylate (Ti(IV) PSS) using sol–gel chemical route with enhanced properties. PTPSS has been characterized by using Fourier Transform Infrared Spectroscopy (FT-IR), X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Energy dispersive X-ray (EDAX), thermo gravimetric analysis (TGA-DTG), and Transmission Electron Microscopy (TEM). Ac electrical conductivity studies were also performed. This material possessed electrical conductivity of ${10}^{-3}$ – ${10}^{-6}$${\text{Scm}}^{-1}$which falls in the semiconducting range. The frequency (2 × 10⁵ – 1 × 10⁶ Hz) dependent Ac conductivity at room temperature suggests the evidence for the transport mechanism for the conductivity in PTPSS. The structure of the composite cation exchanger extremely supports its conducting behavior.