Syngas conversion by Fischer-Tropsch synthesis (FTS) is characterized by a wide distribution of hydrocarbon products ranging from one to a few carbon atoms. Reported here is that the product selectivity is effectively steered toward ethylene by employing the oxide-zeolite (OX-ZEO) catalyst concept with ZnCrO -mordenite (MOR). The selectivity of ethylene alone reaches as high as 73 % among other hydrocarbons at a 26 % CO conversion. This selectivity is significantly higher than those obtained in any other direct syngas conversion or the multistep process methanol-to-olefin conversion. This highly selective pathway is realized over the catalytic sites within the 8-membered ring (8MR) side pockets of MOR via a ketene intermediate rather than methanol in the 8MR or 12MR channels. This study provides substantive evidence for a new type of syngas chemistry with ketene as the key reaction intermediate and enables extraordinary ethylene selectivity within the OX-ZEO catalyst framework.