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This study investigates bimetallic and multimetallic catalysts tailored for the reverse water gas shift (RWGS) reaction. Promoting with potassium and iron, while maintaining a constant copper content of 15 wt% on γ-alumina, revealed that bimetallic catalysts containing 7.5 wt% iron and 5 wt% potassium exhibit superior catalytic activity and stability. Among the multimetallic catalysts, the optimal composition was found to be in the 15 wt% Cu-5 wt% Fe-2.5 wt% K/γ-Al 2 O 3 catalyst for the RWGS reaction. The prepared catalysts underwent assessments using various techniques such as N 2 adsorption-desorption, XRD, H 2 -TPR, CO 2 -TPD, and FESEM. Stability assessments conducted over 72 hours showcased sustained long-term performance for the optimized catalysts, highlighting the influential role of the hierarchical structure. Mesopores extended the catalyst lifetime by reducing permeation limits, while macropores facilitated diffusion process, enhancing selectivity and stability. This hierarchical design also improved mass transfer, amplifying reaction rates. The synthesized catalysts exhibited exceptional specificity, demonstrating 100 % selectivity for the RWGS reaction. Particularly, under H 2 /CO 2 =1, these catalysts displayed remarkable carbon dioxide conversion rates, indicating potential for enhancing Cu-based catalysts in RWGS reactions by maximizing active sites. [Display omitted] • Catalyst support with the highest surface area was prepared via a sol-gel method. • Effect of hierarchical alumina as catalyst support was studied in RWGS reaction. • CO selectivity was 100 % over 15 wt% Cu-XFe-YK/γ-Al 2 O 3 catalysts (X=Fe%, Y K%). • Cu-based catalysts with Fe and K promoted in the RWGS reaction. [ABSTRACT FROM AUTHOR]