Propane dehydrogenation (PDH) reaction has emerged as one of the most promising propylene production routes due to its high selectivity for propylene and good economic benefits. However, the commercial PDH processes usually rely on expensive platinum-based and poisonous chromium oxide based catalysts. The exploration of cost-effective and ecofriendly PDH catalysts with excellent catalytic activity, propylene selectivity, and stability is of great significance yet remains challenging. Here, we discovered a new active center, i.e., an unsaturated tricoordinated cobalt unit (≡Si-O)CoO(O-Mo) in a molybdenum-doped silicalite-1 zeolite, which afforded an unprecedentedly high propylene formation rate of 22.6 molC3H6 gCo-1 h-1 and apparent rate coefficient of 130 molC3H6 gCo-1 h-1 bar-1 with >99% of propylene selectivity at 550 °C. Such activity is nearly one magnitude higher than that of previously reported Co-based catalysts in which cobalt atoms are commonly tetracoordinated, and even superior to that of most of Pt-based catalysts under similar operating conditions. Density functional theory calculations combined with the state-of-the-art characterizations unravel the role of the unsaturated tricoordinated Co unit in facilitating the C-H bond-breaking of propane and propylene desorption. The present work opens new opportunities for future large-scale industrial PDH production based on inexpensive non-noble metal catalysts.