Mn-, LaMn-and LaCaMn-citrates were synthesized at 60-120 • C in ethylene glycol medium using chlorides or nitrates as metal sources. Their composition, IR spectra and thermal decomposition were studied. Equimolar La/Mn ratio has been established in the complex, prepared from chloride solution with the same initial composition of the metals. In the isolated three-metallic complex the molar ratio of the metals deviates from the composition in the initial solution. The final products of the heating of Mn-and mixed-metal LaMn-citrates at 1000 • C are phase-homogeneous Mn 3 O 4 (hausmannite) and LaMnO 3 respectively. Parasitic phase(s) are observed in La x Ca 1−x Mn y O 3 , produced from LaCaMn-citrate.