The prototypes of lithium batteries with organic electrode materials based on two lithium salts of polyhydroquionones containing azomethine groups and, for a comparison, materials based on the original Schiff base are developed and characterized. Poly[3,6-bis(iminomethylphenylene-1,2-diol)dilithium] and poly[3-(iminomethyl)-6-methylimino-N-(1-phenyl-4-diyl)benzene-1,2-dioldilithium] are synthesized and studied for the first time. For these structures, quantum chemical simulations are carried out for calculating the energy of the addition of lithium atoms which can proceed either to the nitrogen atom of the azomethine group or to the oxygen atom of the carbonyl group. It is shown experimentally that the best capacity and stability characteristics are demonstrated by the polymer poly[3,6-bis(iminomethylphenylene-1,2-diol)dilithium with the initial capacity of 140 mA h/g in the cycling interval of 0.7–4.1 V vs. Li+/Li, which makes it a promising cathodic material for lithium batteries.