TiO2 nanosheets and metal-organic framework (NH2-UiO-66) were effectively coupled via an in‐situ growth strategy to form bifunctional materials for the combined capture and photocatalytic reduction of CO2 under UV–vis light irradiation. This was done to take advantage of the high CO2 adsorption capacity of the MOF and the photocatalytic properties of pre-formed TiO2 nanosheets in a single material. The prepared materials were thoroughly characterized using a variety of techniques. They were subsequently tested for CO2 adsorption and CO2 photocatalytic reduction using a heterogeneous gas/solid set-up to imitate both CO2 capture and fixation in a single process. The adopted synthesis process allowed the development of a tight interaction between TiO2 and NH2-UiO-66 forming a heterojunction, while maintaining both the high CO2 uptake and porosity of NH2-UiO-66. The nanocomposites were proven durable and significantly more efficient in reducing CO2 to CO than their single components. Photocatalytic activity was greatly affected by the nanocomposites composition with the optimum TiO2 content doubling the CO evolution rate compared with the pure TiO2. The improved photoactivity was assigned to the enhanced abundance of long lived charge carriers, as revealed by transient absorption spectroscopy (TAS). This most likely occurred due to the effective charge transfer via interface. A possible mechanism is discussed on the basis of the combined catalytic, spectroscopic and CO2 adsorption results.