Abstract Iron‐doped ordered mesoporous alumina (meso‐FeAl) was synthesized through a “one‐pot” method and used in the synthesis of 1,3‐butadiene (BD) through the oxidative dehydrogenation of 1‐butene by using CO 2 as a soft oxidant. X‐ray diffraction, N 2 adsorption, and transmission electron microscopy results confirmed the ordered mesoporous structure of the meso‐FeAl catalyst with a high specific surface area and a large pore volume. The results also revealed that iron species were highly dispersed inside the alumina matrix. Relative to the Fe 2 O 3 ‐impregnated meso‐Al 2 O 3 catalyst and the conventional Fe 2 O 3 /γ‐Al 2 O 3 catalyst, meso‐FeAl showed excellent catalytic activity, good stability, and high selectivity for the synthesis of BD. The structural properties as well as the form of the iron species existing in the meso‐FeAl matrix positively contributed to the performance of the catalyst.