Hybrid polymers combining P2S5 moieties with oligoether spacers have been prepared, and the conductivities and glass transition temperatures of their solutions of lithium salts have been examined. The materials are highly viscous but mostly not rubbery. A high ambient temperature conductivity of 10−3.9 S cm−1 was obtained with LiTFSI dissolved in the sulfide–PEO matrix. The decoupling of Li+ motion from the polymer segmental motion is demonstrated, suggesting that, in certain cases, the transport number for Li+ ion in the sulfide–PEO matrix will be much higher than in a typical PEO-based salt-in-polymer system.