Functional oxides with spinel and perovskite structures are materials of great interest due to their exceptional physicochemical properties which have spurred the field of many technological applications such as oxide electronics and catalysis. In this work, polycrystalline Co3O4 and LaCoO3-based materials have been investigated to comprehend the relationships between the structure, electrical charge transport, optical properties and surface reactivity as a step towards the design of efficient materials. The influence of the structure on the abovementioned physicochemical properties has been experimentally demonstrated. Detailed investigation of the structure-properties-reactivity relationship was performed in the controlled way. The assessed understudy is a valuable step towards an efficient synthesis of materials with tailored properties.