Manganese(III)-chlorophyll-a [Mn(III)-Chl-a] was synthesized by the reaction of pheophytin-a and manganese(II) acetate and separated by HPCL. Manganese(II)-chlorophyll-a [Mn(II)-Chl-a] was acquired from Mn(III)-chl-a reduced by sodium hydrosulfite (Na2S2O4) in acetone-water. Because Mn(II)-Chl-a is oxidized very easily in the air, Mn (II)-Chl-a was kept under a nitrogen atmosphere and reductant during the spectroscopic measurements. Elemental analysis, absorption and FT-IR spectra proved that the metal Mn-substituted Mg of chlorophyll-a has been successfully performed and possible structure of new complexes was also given. Their formulae are [Mn(II) (chlorophyll-a)] and [Mn(III) (chlorphyll-a) (CH3COO)-(H2O)] respectively.