The deoxydehydration of carbohydrates represents a key target to leverage renewable biomass resources chemically. Using a vanadium(V)‐based catalyst, we demonstrate that it is possible to directly deoxydehydrate cyclic trans‐diol substrates. Accompanying mechanistic characterisation of this process by density functional calculations points to an energetically tractable route for deoxydehydration of cyclic trans‐diol substrates involving stepwise cleavage of the diol C‐O bonds via the triplet state; experimentally, this is supported by light dependence of the reaction. Calculations also indicate that cyclic cis‐diols and a linear diol substrate can additionally proceed by a concerted singlet DODH mechanism. This work potentially opens a new and cost‐effective way to efficiently convert carbohydrates of trans‐diol stereochemistry into alkenes.