Iron-containing HZSM-5 zeolite was first time chosen to couple with Ti-O species. Ti species highly dispersed as nanoclusters or mono-sites on the HZSM-5 zeolite surface. The as-prepared Ti-HZSM-5 sample exhibited enhanced performance for photocatalytic CO2 reduction. Ti-O species and Fe-O species work synergistically upon UV-light irradiation.