In this contribution we present a soft matter solid electrolyte which was obtained by inclusion of a polymer (polyacrylonitrile, PAN) in LiClO4/LiTFSI–succinonitrile (SN), a semi-solid organic plastic electrolyte. Addition of the polymer resulted in considerable enhancement in ionic conductivity as well as mechanical strength of LiX–SN (X=ClO4, TFSI) plastic electrolyte. Ionic conductivity of 92.5%-[1M LiClO4–SN]:7.5%-PAN (PAN amount as per SN weight) composite at 25°C recorded a remarkably high value of 7×10−3 Ω−1 cm−1, higher by few tens of order in magnitude compared to 1M LiClO4–SN. Composite conductivity at sub-ambient temperature is also quite high. At −20°C, the ionic conductivity of (100− x)%-[1M LiClO4–SN]:x%-PAN composites are in the range 3×10−5–4.5×10−4 Ω−1 cm−1, approximately one to two orders of magnitude higher with respect to 1M LiClO4–SN electrolyte conductivity. Addition of PAN resulted in an increase of the Young's modulus (Y) from Y →0 for LiClO4–SN to a maximum of 0.4MPa for the composites. Microstructural studies based on X-ray diffraction, differential scanning calorimetry and Fourier transform infrared spectroscopy suggest that enhancement in composite ionic conductivity is a combined effect of decrease in crystallinity and enhanced trans conformer concentration.