The effect of water on "antiplasticization" and plasticization of green and roasted coffee was studied by textural analysis, sorption isotherms, differential scanning calorimetry (DSC), and nuclear magnetic resonance (NMR). From BET monolayer value to a(w) = 0.61 and 0.75 for green and roasted coffee, respectively, the solid matrix hydration occurred and water induced hardening. Very short NMR T(2) values and the concomitant absence of any DSC endothermic peak assignable to water freezing were observed at these a(w) values. When solid matrix hydration was completed, water started to act as a plasticizing agent, the compressive modulus started to decrease, and NMR revealed the appearance of a new proton pool with increased mobility. According to DSC, only when the plasticizing effect became important did water present enough mobility to freeze. Above this moisture value (a(w) = 0.78 and 0.86 for green and roasted coffee, respectively), water determined a decrease of bean hardness and a further decrease of the elastic modulus.