The structure of diaquo(1,2-dimethoxyethane)lithium tetraphenylborate, [Li(CH3OCH2-CH2OCH3)(H 2O)2][BPh4], has been determined at 293 K. The compound crystallizes in the trigonal P3(1)21 space group (a = b = 9.9760(14), c = 23.662(5)). Both the lithium and the boron sit on a twofold rotation axis. The lithium is coordinated to two water oxygens and both ether oxygens of the 1,2-dimethoxyethane group. The coordination geometry is significantly distorted from a tetrahedron by the twisting of the plane containing the two water oxygens and the lithium relative to that containing the two 1,2-dimethoxyethane oxygens and the lithium. The five-membered chelate ring formed by chelation of the 1,2-dimethoxyethane to the lithium is a twist envelope consistent with the twofold rotation axis passing through the lithium and the center of the carbon-carbon bond of the 1,2-dimethoxyethane. Hydrogen bonding between each water hydrogen and a phenyl group of the tetraphenylborate is observed and results in a linear polymeric structure.