A search of the Cambridge Structural Database (CSD) yielded a data set of 375 purely molecular structures to be used for study of methanol solvates. Five different hydrogen bond environments of methanol were defined and their occurrence within this data set investigated. Methanol is most commonly found to be either, a proton donor or simultaneously both a donor and single acceptor. Analysis with VISTA and Isogen provided statistical information concerning the hydrogen bond lengths and angles. A common feature of methanol in these structures is that it adopts a hydrogen-bonding motif similar to that found in liquid methanol. A common feature of the host molecules is that they exhibit more acceptor than donor functionality although there is no correlation between the extent of this mismatch and the tendency for methanolate formation. Finally 21 structural pairs in which a single host molecule has both a known solvated and unsolvated form were identified and compared. © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.