<p>The reduction of CO₂ to gaseous fuels using photoelectrocatalysis is an effective way to alleviate the energy crisis and the greenhouse effect, and thus has received much attention in recent years. This study employs anodization and chemical deposition methods to load In₂O₃ on TiO₂ nanotube arrays (TNTAs). The microstructure and morphology of the samples were characterized using field emission scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The test results confirm the successful preparation of In₂O₃/TNTAs composites. The results proved that the In₂O₃/TNTAs composites have been successfully prepared. Under the irradiation of ultraviolet light, a gas–solid micro-interface photoelectrocatalytic reaction system with "double-coupling effect" was constructed to organically combine the photocatalytic reduction of CO₂ with the photocatalytic oxidation of typical VOCs (xylene) to realise carbon recycling. The results showed that the photoelectrocatalytic end products were mainly CO and CH₄, and the reaction system had better selectivity for CO; the yields of CO and CH₄ in the mixed CO₂-Xylene system were larger than those in the single-component systems of CO₂ or Xylene, and the yields of CO and CH₄ could reach 0.221&#xa0;µmol·h⁻¹·cm⁻² and 0.007&#xa0;µmol·h⁻¹·cm⁻², respectively. The degradation rate of Xylene was 82.37% at an applied potential of 1.0&#xa0;V (vs. Ag/AgCl) and a light exposure time of 8&#xa0;h. The degradation rate of xylene was 82.37% at an applied potential of 1.0&#xa0;V and a light exposure time of 8&#xa0;h. This study utilises the "double-coupling effect" to realise the carbon cycle and provides a new solution to address both greenhouse gases and air pollutant gases.</p>