The reduction of CO₂ is relevant for the production of compounds as part of the carbon capture and utilization research approaches. Thus, photocatalytic reduction of CO₂ over a tailored BiOCl-based photocatalyst (BTEG) was tested under UV light (365 nm). BTEG was synthesized in the presence of triethylene glycol, which gave 4-nm crystallites, much smaller than the 30 nm crystallites of commercial BiOCl. Commercial BiOCl reduced CO₂ mainly to methane with a minor fraction of ethanol, and was inactivated after 20 h. BTEG was a more active catalyst for CO₂ photoreduction, producing approximately equal amounts of methane, methanol, and ethanol while consuming 0.38 µmol g⁻¹ h⁻¹ of CO₂ before the experiment was stopped after 43 h, with the catalyst still active. The different products formed by the BTEG photocatalyst samples were tentatively ascribed to its greater content of {110} facets. Thus, in addition to band-gap tuning, the relative fractions of BiOCl facets had a key role in the effective photocatalytic reduction of CO₂, and the BiOCl-based BTEG catalyst promoted the formation of important compounds as methanol and ethanol.