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Abstract. The systems poly(butadiene-co-acrylonitrile) (PBAN) -lithium salts have been studied by means of X-ray and IR spectroscopy, optical microscopy and ac-and dc-conductivity measurements. X-ray and microscopy studies have confirmed that PBAN dissolves LiC104 up to [CN]/[Li] = 2: 1. IR spectra of the samples with LiAsF 6, LiCF3SO 3 and LiC104 have indicated the coordination between Li § and the polar CN groups of PBAN. So, PBAN was found to be a suitable polymer matrix for SPE. The polymer films exhibited predominant ionic conductivity. Measurements of conductivity and Li transport numbers versus temperature over a wide range of salt concentrations revealed the existence of two concentration regions (within the limits of salt solubility) corresponding to liquid-like and glass-like ion transport mechanisms. New solid polymer electrolyte with lithium single-ion conductivity of 10 .3 S cm "1 at 25 -95 ~ was obtained.