Crystal　facet　and　defect　engineering　are　crucial　for　designing　heterogeneous　catalysts.　In　this　study,　different　solvents　were　utilized　to　generate　NiO　with　distinct　shapes　(hexagonal　layers,　rods,　and　spheres)　using　nickel-based　metal-organic　frameworks　(MOFs)　as　precursors.　It　was　shown　that　the　exposed　crystal　facets　of　NiO　with　different　morphologies　differed　from　each　other.　Various　characterization　techniques　and　density　functional　theory　(DFT)　calculations　revealed　that　hexagonal-layered　NiO　(NiO-L)　possessed　excellent　low-temperature　reducibility　and　oxygen　migration　ability.　The　(111)　crystal　plane　of　NiO-L　contained　more　lattice　defects　and　oxygen　vacancies,　resulting　in　enhanced　propane　oxidation　due　to　its　highest　O2　adsorption　energy.　Furthermore,　the　higher　the　surface　active　oxygen　species　and　surface　oxygen　vacancy　concentrations,　the　lower　the　C−H　activation　energy　of　the　NiO　catalyst　and　hence　the　better　the　catalytic　activity　for　the　oxidation　of　propane.　Consequently,　NiO-L　exhibited　remarkable　catalytic　activity　and　good　stability　for　propane　oxidation.　This　study　provided　a　simple　strategy　for　controlling　NiO　crystal　facets,　and　demonstrated　that　the　oxygen　defects　could　be　more　easily　formed　on　NiO(111)　facets,　thus　would　be　beneficial　for　the　activation　of　C−H　bonds　in　propane.　In　addition,　the　results　of　this　work　can　be　extended　to　the　other　fields,　such　as　propane　oxidation　to　propene,　fuel　cells,　and　photocatalysis.　©　2024　Elsevier　B.V.