. La1-xCexCoO3 (x=0, 0.2, and 0.4) perovskite-type mixed oxides using polyvinyl alcohol (PVA) as complexing agent at two molar ratio of metal ion to PVA (1:1 and 1:2) were successfully prepared by sol-gel process. The precursor included lanthanum (II) nitrate hexahydrate, cerium (II) nitrate hexahydrate, and cobalt (II) nitrate hexahydrate where polyvinyl alcohol was added as complexing agent. The suitable condition of Cerium (Ce) substitution and PVA molar ratio were established for further application in hydrocarbon conversion to high value added products. TGA thermogram of as-prepared precursor showed that PVA absolutely decomposed at temperature higher than 500°C. XRD patterns of calcined catalyst showed both LaCoO3 rhombohedral and CeO2 cubic structures that confirmed the formation of mixed crystal structure. Nevertheless, Co3O4 slightly appeared with low peak intensity which came from the oxidation reaction of as-prepared catalyst during calcinations. XRD showed that PVA did not effect to crystal structure of synthesized catalyst. Higher PVA content added in the precursor cause the reduction of crystal growth of catalyst in calcinations step. In contrast, morphology of catalyst is directly related with PVA content such that the spongy and sheet-like structure were formed with increasing PVA content which prevented the agglomeration of particles. The results showed that PVA content play an important role in morphology of perovskite-type mixed oxide catalysts but did not affected to their crystal structures.