We have shown that crown ether complexes with the lithium salt, lithium bis-(trifluoromethanesulphonyl) imide (LiTFSI), are plastic crystals as evidenced by DSC and their mechanical properties. The conductivity of the complexes was measured and found to vary as a function of crown ether:salt molar ratio. Our study of the (18-Crown-6)–LiTFSI (1/1) solid complex showed that it has a high conductivity reaching ∼10−4 Scm−1 at 50°C and an electrochemical stability of over 4V enabling its use in a lithium-metal battery. A lithium battery with 1:1 (18-Crown-6)–LiTFSI as electrolyte was assembled, tested, and found to exhibit reversible Li+ transport.