Dilithium benzenedipropiolate was prepared and investigated as a potential negative electrode material for secondary lithium-ion batteries. In addition to the expected reduction of its carbonyls, this material can reduce and reversibly oxidize its unsaturated carbon–carbon bonds leading to a Li/C ratio of 1/1 and a specific capacity as high as 1363 mAh g–1: the highest ever reported for a lithium carboxylate. Density functional theory calculations suggest that the lithiation is preferential on the propiolate carbons.