Our research focuses on special class of oxides with complex structure, the AMO3-x perovskites. They exhibit a wide range of unique properties, including magnetic phenomena, superconductivity, ferroelectricity and ionic conductivity, to mention a few. Among the numerous methods developed for synthesizing metal oxides the organometallic molecular precursor way has been regarded as one of the most convenient and practical techiques, because it provides good control over purity,composition, homogeneity, phase and microstructure of the ceramic products, than those employed in traditional solid-state synthesis. We have been interested for a few years in the synthesis of metal oxides, using new inorganic, coordination precursors via decomposition methods, taking profit of the tools of coordination chemistry. In recent decade has been extensively documented, that starting materials could influence on the microstructure of inorganic solids, so we decide to develop our research to the synthesis of organometallic molecular precursors with proper ratio of metals, that provide a way for the design of new solid materials with contolling their nanocrystal size and morphology. A series of perovskite oxides with general formulae ABO3-x (where A=Co, B=Ba, Sr, Ca, La ) have been synthesized by thermal decomposition method using some heterometallic 2,3- pyridinedicarboxylate complexes of composition [CoMII, III (2,3-PDC)n(H2O)m] -PDxHC2 –Ois (where 2,3 dianion of 2,3-pyridinedicarboxylic acid, MII=Ba2+ (1),Sr2+ (2), n=2, m=5, x=3; MII=Ca2+ (3), n=2, m=5, x=1; MIII=La3+ (4), n=m=3, x=0)[8], as coordination molecular precursors. The structure and composition of starting 2,3-pyridinedicarboxylates have been confirmed by single crystal X-ray diffraction analysis. All complexes (1-4) have polymeric structures, where 2,3- PDC ligand show different coordination modes, that provide ndimensional structures assembling. Therefore, using molecular structure design approach, thermal decomposition and X-ray powder diffraction methods, the suitability of synthesized coordination solids for mixed oxide preparation has been revealed with potential applications in eletroceramics, catalysis and sensor applications.