Fuels derived from CO₂ can contribute to neutralize the carbon balance in the atmosphere and can be converted into easily transportable liquid chemicals, such as methanol (MeOH) or ethanol (EtOH). In this work, a composite prepared from graphene oxide (GO) and titanium dioxide (TiO₂) is applied to the photocatalytic water reduction of CO₂ into renewable fuels under UV/vis light irradiation. The pH was identified as a key variable towards selective MeOH formation. The prepared GO–TiO₂ composite exhibited superior photocatalytic activity for EtOH production (144.7 μmol g⁻¹ h⁻¹) at pH 11.0 and for MeOH production (47.0 μmol g⁻¹ h⁻¹) at pH 4.0. The effect of copper species in the GO–TiO₂ composite is also assessed and its influence on the photocatalytic reaction inferred. The photocatalysts prepared with copper nitrate as copper precursor exhibited the highest rate of MeOH production at pH 11.0. Accordingly, a conceptual scheme in which the photogenerated electrons are used to reduce CO₂ is proposed.