Structural, thermal and electrical transport in PEO-LiCF3SO3 solid polymer electrolyte dispersed with Li+ - NASICON crystallites has been assessed. Fine submicron crystallites of LiTi2(PO4)(3) (LIP) were added in appropriate amount during solution casting of the polymer films. Thus the compositions 95[PEO1-x-LTPx]-5LiCF(3)SO(3) have been synthesized for a wide range of LTP content (x = 0-0.9). Electrical conductivity increases with LTP content monotonically. Highest room temperature conductivity of similar to 7 x 10(-5) Omega(-1) cm(-1) has been obtained for the sample with x = 0.9 of LTP which is similar to 43 times higher than that of the sample with no LTP content. FE-SEM investigations performed on pellets with higher LTP content suggest uniform distribution of LTP particles in the polymer matrix. Preliminary investigations reveal that mechanism of electrical transport in SPE-LTP hybrid composites is greatly influenced by LTP content.