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Note: The source of the background picture is from website. [Display omitted] • K 3 PO 4 could adjust Cu+/(Cu0 + Cu+) and promote catalytic performance greatly. • By regression analysis, Fe2+, Cu0, and medium base site show linear relation to C 2+ OH STY. • Significance level of above three factors follows Cu0＞Fe2+＞medium base sequence. • Conversion of Fe0 to Fe 3 C or Fe 3 O 4 leads to activity decrease. CO 2 hydrogenation to C 2+ OH is an effective way to diminish CO 2 emissions. Although challenges still exist in large-scale applications, CuFeZn catalysts attract extensive attention due to their low-cost. Herein, CuFeZn catalysts are modified by different amounts of K 3 PO 4 , (KP) 0.1 CuFeZn exhibits an excellent catalytic performance (total alcohols selectivity of 15.76 % at CO 2 conversion of 38.10 %, C 2+ OH/ROH fraction of 94.23 %, and C 2+ alcohols space–time-yield (STY) of 53.81 mg·mL−1·h−1). Combined with a series of characterization results, it is found that the effect of K 3 PO 4 is complex, and the proportion of Fe2+, Cu0 and medium base shows perfect linear relation to STY of C 2+ OH. The significance level of the above three factors is in the following sequence: Cu0＞Fe2+＞medium base. The introduction of K 3 PO 4 decreases the proportion of Fe2+ (active site for RWGS, the competitive reaction for C–C coupling) and increases the proportion of Cu+/(Cu++Cu0) (Cu+ is the active site for C–C coupling) due to the synergistic effect of Cu0 and Cu+, thereby improving the synthesis of C 2+ OH. Moreover, conversion of Fe0 to Fe 3 C or Fe 3 O 4 plays negative roles in the stability of the catalysts. [ABSTRACT FROM AUTHOR]