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.