Comprehensive SummaryOxidative dehydrogenation of propane has been an ever‐growing field for propylene production due to its exothermic properties, of which overoxidation is the major drawback, with CO and even CO2 as undesired by‐products. For the purpose of getting higher propylene selectivity as well as yield, herein we report Ni single atoms supported on calcium aluminate as an efficient catalyst candidate for propane oxidative dehydrogenation. Beneficial from higher valence states of Ni1 species, it shows 2~3 times as much propylene selectivity as that of Ni nanoparticles. About 14.2 % C3H6 yield with 47.3 % propylene selectivity have been achieved on the 2% Ni single atom catalyst and a good stability during 20 h test can be obtained as well.This article is protected by copyright. All rights reserved.