The effect of Zr addition into malic acid complex was examined for the purpose of the improvement of microstructure and specific surface area of CaFe₂O₄. The CaFe₂O₄ phase could be obtained for both unadded and Zr-added (5 and 10 mol % with respect to Fe) system by calcination of precursor derived from malic acid complex at 700°C which is almost 200°C lower than that of conventional solid-state reaction method. Among the examined products, only the 5 mol % Zr-added product revealed characteristic smaller grains connected three dimensional porous structures resulting in higher specific surface area compared with unadded and 10 mol % Zr-added products. XPS measurements revealed that there are no notable changes in valence state for all constituent elements. The obtained final product of 5 mol % Zr-added CaFe₂O₄ is worth further investigate for various application from a view point of improved higher specific surface area and characteristic microstructure as well as the functionality of the material itself.