​We report the synthesis of a highly active, selective and stable catalyst for the hydrogenation of CO2 to short chain olefins in one single step by using a Metal Organic Framework as catalyst precursor. By studying the promotion of the resulting Fe(41 wt %)-carbon composites with different elements (Cu, Mo, Li, Na, K, Mg, Ca, Zn, Ni, Co, Mn, Fe, Pt and Rh) we have found that only K is able to enhance olefin selectivity. Further catalyst optimization in terms of promoter loading results in catalysts displaying unprecedented C2-C4 olefin space time yields: 33.6 mmol·gcat-1·h-1 at XCO2 = 40%, 320 ⁰C, 30 bar, H2/CO2 = 3, and 24000 mL·g-1·h-1. Extensive characterization demonstrates that K promotion affects catalytic performance by: (i) promoting a good balance between the different Fe active phases playing a role in CO2 hydrogenation, namely iron oxide and iron carbides and by (ii) increasing CO2 and CO uptake while decreasing H2 affinity, interactions responsible for boosting olefin selectivity. ​