The enhanced laboratory and field emergence characteristics of osmo- and halo-primed tomato seeds (cv. Pusa Ruby) were related to changes in hydration–dehydration kinetics, modified sorption properties and nuclear magnetic resonance (NMR) relaxation behaviour of humidified and imbibed seeds. Water sorption isotherms were constructed for primed and unprimed seeds by equilibrating to different water activities (aw) at 25°C. Analysis of the isotherms by the D'Arcy–Watt equation revealed that priming reduced the number of strong binding sites and the associated water content, and increased significantly the number of weak binding sites and the associated water content. This redistribution of water, which increased the availability of seed water, may be the reason for the higher speed of germination of primed seeds. The changes in transverse relaxation time (T2) of seed water and its components, measured in vivo using nuclear magnetic resonance spectroscopy, showed interesting differences between primed and unprimed seeds. With an increase in humidification time, the T2 of primed seeds could be resolved into three components with varying mobilities, while the control seeds had only two components until 10 d of humidification. During imbibition, the third component appeared after 2 and 6 h in primed and control seeds, respectively. This component disappeared after the germination process started in all treatments. The third fraction, with very low molecular mobility, which accounted for about 40% of the proton population, was assigned to hydration water of macromolecules. Hence, we propose that better performance of primed seeds may be attributed to the modifications of seed water-binding properties and reorganization of seed water during imbibition, so as to increase the macromolecular hydration water required for various metabolic activities related to the germination process.