Only limited enhancement in room-temperature ionic-conductivity for poly(ethylene oxide), PEO, based electrolytes is possible due to coupling between ionic-conductivity and segmental relaxation. In the present study, we have achieved ionic-conductivity of 1.07 × 10⁻³ and 6.20 × 10⁻⁴ S cm⁻¹ at 313 and 298 K, respectively, by adding 45 wt% of succinonitrile (SN) in PEO having low LiTFSI loading (Li : EO = 1 : 20). This enhancement in the ionic-conductivity is attributed to faster ion transport (diffusion coefficient, D = 3.63 × 10⁻⁵ cm² s⁻¹) occurring through the ion-transport channels as confirmed by positron annihilation lifetime spectroscopy. The ionic-transport through these channels is observed to be highly decoupled from the segmental relaxations as confirmed using broadband dielectric spectroscopy through Ratner's approach. The observed decoupling of ionic-conductivity from PEO segmental relaxation in PEO–SN composite-based electrolytes would be useful to design rather inexpensive all solid-state polymer electrolytes for Li ion batteries.