Herein, we report a highly selective production route for butadiene from γ‐valerolactone over zeolite catalysts. The catalytic performance of eight zeolites with different framework topologies were compared, revealing that zeolites with narrower 10‐membered ring channels exhibit enhanced selectivity of butadiene. Specifically, ZSM‐35 and ZSM‐22, featuring the narrowest 10‐membered ring channels, demonstrate the highest butadiene selectivity to 61% and 59%, respectively. Notably, surface passivation of ZSM‐35 leads to a remarkable increase in butadiene selectivity to 82%, maintaining a 99% conversion. Additionally, we propose a reaction network and identify cyclopentenone as a key intermediate in the transformation of γ‐valerolactone to butadiene. Both experimental and theoretical results conclude that confinement effect of 10‐membered ring channels improves the selectivity of butadiene.