Photochemical conversion of CO₂ into high-value C₂₊ products is difficult to achieve due to the energetic and mechanistic challenges in forming multiple C-C bonds. Herein, an efficient photocatalyst for the conversion of CO₂ into C₃H₈ is prepared by implanting Cu single atoms on Ti_0.91O₂ atomically-thin single layers. Cu single atoms promote the formation of neighbouring oxygen vacancies (V_Os) in Ti_0.91O₂ matrix. These oxygen vacancies modulate the electronic coupling interaction between Cu atoms and adjacent Ti atoms to form a unique Cu-Ti-V_O unit in Ti_0.91O₂ matrix. A high electron-based selectivity of 64.8% for C₃H₈ (product-based selectivity of 32.4%), and 86.2% for total C₂₊ hydrocarbons (product-based selectivity of 50.2%) are achieved. Theoretical calculations suggest that Cu-Ti-V_O unit may stabilize the key *CHOCO and *CH₂OCOCO intermediates and reduce their energy levels, tuning both C₁-C₁ and C₁-C₂ couplings into thermodynamically-favourable exothermal processes. Tandem catalysis mechanism and potential reaction pathway are tentatively proposed for C₃H₈ formation, involving an overall (20e⁻ – 20H⁺) reduction and coupling of three CO₂ molecules at room temperature.