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.