Synthesis of ethanol from non-petroleum carbon resources via syngas (a mixture of H₂ and CO) is an important but challenging research target. The current conversion of syngas to ethanol suffers from low selectivity or multiple processes with high energy consumption. Here, we report a high-selective conversion of syngas into ethanol by a triple tandem catalysis. An efficient trifunctional tandem system composed of potassium-modified ZnO–ZrO₂, modified zeolite mordenite and Pt–Sn/SiC working compatibly in syngas stream in one reactor can afford ethanol with a selectivity of 90%. We demonstrate that the K⁺–ZnO–ZrO₂ catalyses syngas conversion to methanol and the mordenite with eight-membered ring channels functions for methanol carbonylation to acetic acid, which is then hydrogenated to ethanol over the Pt–Sn/SiC catalyst. The present work offers an effective methodology leading to high selective conversion by decoupling a single-catalyst-based complicated and uncontrollable reaction into well-controlled multi-steps in tandem in one reactor.