The direct syngas conversion to olefins, aromatics and other hydrocarbons has attracted increasing attention while unraveling the complex reaction mechanism is of great challenge. It was recently demonstrated that zinc-exchanged zeolites could selectively convert syngas to alkanes, particular ethane, and [Zn–O–Zn] motif is likely the intrinsic active site. The underlying reaction network however remains ambiguous. Herein, we proposed a reaction mechanism for the direct conversion of syngas to light alkanes including methane and ethane using density functional theory calculations in periodic [Zn–O–Zn]-ZSM-5 zeolite model. The evolution of syngas to ethane follows the sequence of CO → CH2O → CH2CO → CH3CHO → C2H6. The activation of CO to formaldehyde initiates the reaction. The [Zn–O–Zn] site can readily be reduced by CO to [Zn–Zn] site, which either inserts aldehydes to form [Zn–O-CnH2n-Zn] motif for chain propagation to higher aldehydes, or converts aldehydes to alkanes for chain termination. Ketene is the first intermediate after the C–C bond coupling between [Zn–O–CH2–Zn] and CO. Both the structures and the evolution sequence of the involved intermediates in the proposal (formyl, methylene, acetyl, ethyl) coincide quite well with experimentally quasi in-situ characterized results. The proposed reaction network consisting of initiation, propagation and termination sub-cycles unifies the formation pathway of methane, ethane, and higher alkanes, and bears some resemblance to the Fischer-Tropsch synthesis for syngas conversion. This theoretical work thus further vindicates the critical role of [Zn–O–Zn] site and may proffer some implications to tailor alkane selectivity in metal-exchanged zeolites for syngas conversion.