Conversion of CO2/H2 and CO/H2 into α-olefins via Fischer-Tropsch synthesis (FTS) reaction has stimulated great interest. Herein, iron-based catalysts were developed to produce α-olefins with a tailor-made manner. As-synthesized 1.5Na-Fe1Zn1 exhibited high activity for CO2 conversion, high selectivity toward C2-C5 light olefins along with stable 1000 h run. Separate catalytic cracking of C5+ products over ZSM-5 nanosheet promoted light olefins selectivity up to 64.6 %, benefiting from the elimination of hydrogenation reaction. Interestingly, Na2S showed different effects in CO2-FTS and CO-FTS over iron-based catalysts. In detail, Na2S significantly suppressed catalytic activity and increased selectivity toward alkanes/CO in CO2-FTS reaction. However, it can surprisingly improve catalyst stability in CO-FTS reaction, leading to high activity at about 96 % CO conversion and high selectivity to long-chain C4+ olefins at about 65.4 %. In addition, it was demonstrated that H2O accumulation hindered H2/CO adsorption and dissociation, subsequent hydrogenation into CHx, and their carbon–carbon coupling, which resulted in catalyst deactivation and selectivity shifting toward CH4 and CO in atmospheric pressure CO2-FTS reaction.