The singly and doubly hydrated complexes of the α and β anomers of a systematically varied set of monosaccharides, O-phenyl D-gluco-, D-galacto-, L-fuco- and D-xylopyranoside, have been generated in a cold molecular beam and probed through infrared-ultraviolet double resonance ion-dip (IRID) spectroscopy coupled with quantum mechanical calculations. A new 'twist' has been introduced by isotopic substitution, replacing H(2)O by D(2)O to separate the carbohydrate (OH) and hydrate (OD) vibrational signatures and also to relieve spectral congestion. The new spectroscopic and computational results have exposed subtle aspects of the intermolecular interactions which influence the finer details of their preferred structures, including the competing controls exerted by co-operative hydrogen bonding, bi-furcated and OH-π hydrogen bonding, stereoelectronic changes associated with the anomeric effect, and dispersion interactions. They also reassert the operation of general 'working rules' governing conformational change and regioselectivity in both singly and doubly hydrated monosaccharides.