In this work, we have demonstrated the fabrication of a Co3O4 NP-coated TiO¬2 NWs with enzyme surface functionalization, which represents an artificial metabolism-inspired photoelectrochemical biomolecule probing design. Driven by the solar energy, the oxidative species formed on the Co3O4-TiO2 photoanode serve as a charge shuttle between the photo-excited electrode surface and the redox enzyme that mimics a simple metabolism process, during which the enzyme can effectively function with high efficiency, thus leading to excellent sensitivity for metabolically-important biomolecules. As proofs of concept, the successful probing of the ATP or cholesterol levels has been achieved using this Co3O4-TiO2-enzyme platform, with the capability of measurement in serum samples or from cell extracts.