Molybdenum catalysts bearing ONO, ON(N)O, ON(O)N and ON(S)O ligands were studied for catalytic deoxydehydration of vicinal diols. The complex bearing N',N'‐bis(2‐hydroxy‐3,5‐dimethylbenzyl)‐N,N‐dimethylethylenediamine ligand afforded full conversion and up to 97% selectivities towards alkenes, when aliphatic vicinal diols were subjected to the reaction at 5 mol% catalyst loading.