The initial stages of Umbilicaria aprina Nyl. hydration (starting from the hydration level Δm/m0 = 0.048 ± 0.004) were observed using hydration kinetics, sorption isotherm and proton NMR. The thalli were hydrated from gaseous phase. The total saturation hydration level obtained at the relative humidity p/p0 = 100% was Δm/m0 = 0.848 ± 0.009. The hydration courses revealed i) a fraction of very tightly bound water (Δm/m0 = 0.054 ± 0.011, short hydration time constant, thyd), ii) a fraction of tightly bound water [Δm/m0 = 0.051 ± 0.038, thyd = (4.7 ± 2.6) h], and iii) a loosely bound water pool [thyd = (31.0 ± 1.9) h] for higher values of target humidity. The sorption isotherm of U. aprina was fitted well using Dent model. The relative mass of water saturating primary binding sites was ΔM/m0 = 0.054, which is close to the water fractions. Proton FIDs detected (i + ii) the immobilized tightly bound water fraction, L1, and iii) the mobile, loosely bound water pool L2. The hydration dependence of the proton liquid signal suggests the presence of a significant contribution from a water soluble solid fraction in the thallus. Sorption isotherm fitted to NMR data showed the absence of ‘sealed’ water fraction trapped in pores of the thallus.