<p>Catalytic syngas conversion has the potential to improve the sustainability of chemical products. However, balancing high catalytic activity with selectivity is challenging because the complex interactions among intermediates across various active sites can trigger competing reactions. To address this challenge, we introduce a catalytic shunt strategy that redirects intermediates in a multifunctional catalytic system to guide interdependent reaction pathways. The key to this catalytic shunt strategy is modulating the adsorption of the intermediates across different activity domains. By tuning Mo–O coordination numbers of single atoms in a bifunctional catalyst, we achieve over 80% selectivity for aromatics and a carbon monoxide conversion surpassing 70%, with aromatics yields of over 40%. By absorbing the intermediates on the first activity domain, the shunt pathway prevents their participation in subsequent reactions, thereby boosting methane production with selectivity above 93% and carbon monoxide conversion exceeding 50%. This catalytic shunt strategy also showcases versatility across other bifunctional systems for producing gasoline and light olefins. Overall, this study provides a viable approach for tackling the activity–selectivity trade-off in catalytic syngas conversion, removing a major barrier preventing its practical implementation.</p>