Conformational flexibility and non‐covalent interactions determine the structure and activity of molecules in biological processes. In this work, the hydrogen bonding networks of the polyol ribitol have been determined for the first time using a combination of laser ablation and broadband rotational spectroscopy. Five conformations of ribitol have been identified, two with extended carbon chains and three with bent chains. All conformations are stabilized by sequential hydrogen bonding networks of either four or five intramolecular O‐H···O bonds in a clockwise or counter‐clockwise arrangement. The hydrogen bonding patterns are related to the extended or bent‐chain conformations of ribitol, and involve 2OH‐4OH or 2OH‐5OH linkages, respectively. Interestingly, all hydrogen bonds wrap round the carbon backbone of ribitol rather than being located above or below it as it happens for other polyols and cyclic sugars.