Metal-free, Cu(II)- or Zn(II) tetrakis [4-(2,4-bis-(1,1-dimethylpropyl)phenoxy)]phthalocyanines loaded over TiO2 (anatase) proved to be active in the photoreduction of CO2 to formic acid (HCO2H) in water under UV-vis light. CuPc/TiO2 is catalyst of choice, allowing to reach a maximum yield of HCO2H, unequalled by any other similar catalytic systems. Because of their low environmental impact, low potential cost, and efficient power conversion, these multipurpose materials show promise in the setup of sustainable methods for CO2 valorization. (C) 2014 Elsevier B.V. All rights reserved.