Gold nanoparticles (NPs) supported on hydrotalcite (Au/HT) are highly active and selective catalysts for the continuous, gas‐phase, non‐oxidative dehydrogenation of bioderived C₂–C₄ alcohols. A sharp increase in turn over frequency (TOF) is noted when the size of Au NPs is less than 5 nm relating to the strong synergy between metallic Au NPs and the acid–base groups on the support surface. It is shown that catalytic activity depends critically on Au NP size, support composition, and support pretreatments. A reaction pathway elucidated from kinetic isotope effects suggests that the abstraction of β‐H by Au NPs (C−H activation) is the rate‐determining step in the dehydrogenation of bioderived C₂–C₄ alcohols.