The review summarizes literature data on the thermal decomposition of ferrous oxalate with the formation of Fe, FeO, Fe2O3, Fe3O4, Fe3C, and other products. Historical evolution of views on the ways and mechanisms of oxalate thermolysis is traced. The current state of the art is analyzed from the perspective of FeC2O4·2Н2O0 compound for the synthesis of lithium iron phosphate LiFePO4, which is a promising cathode material for lithium-ion batteries.