The structure of 2‐hydroxymethylpyridine N‐oxide was determined from X‐ray diffractometer data by a direct method. The compound crystallizes in the monoclinic space group P21/c with cell dimensions a = 7.079, b = 8.046, c = 10.599 Å, cosβ = −0.2252. A total of 1241 independent reflections were refined to an R value of 0.06. The N‐O dative bond has a length of 1.321 Å and the dative oxygen is bonded to a hydroxyl group on a symmetry related molecule by an inter‐molecular hydrogen bond. The structure corroborates recent findings concerning the relationship between the strength of hydrogen bonding to a dative oxygen and the length of the NO dative bond.