Armenite, ideal formula BaCa 2Al 6Si 9O 30·2H 2O, and its dehydrated analog BaCa 2Al 6Si 9O 30 and epididymite, ideal formula Na 2Be 2Si 6O 15·H 2O, and its dehydrated analog Na 2Be 2Si 6O 15 were studied by low-temperature relaxation calorimetry between 5 and 300 K to determine the heat capacity, C p, behavior of their confined H 2O. Differential thermal analysis and thermogravimetry measurements, FTIR spectroscopy, electron microprobe analysis and powder Rietveld refinements were undertaken to characterize the phases and the local environment around the H 2O molecule. The determined structural formula for armenite is Ba 0.88(0.01)Ca 1.99(0.02)Na 0.04(0.01)Al 5.89(0.03)Si 9.12(0.02)O 30·2H 2O and for epididymite Na 1.88(0.03)K 0.05(0.004)Na 0.01(0.004)Be 2.02(0.008)Si 6.00(0.01)O 15·H 2O. The infrared (IR) spectra give information on the nature of the H 2O molecules in the natural phases via their H 2O stretching and bending vibrations, which in the case of epididymite only could be assigned. The powder X-ray diffraction data show that armenite and its dehydrated analog have similar structures, whereas in the case of epididymite there are structural differences between the natural and dehydrated phases. This is also reflected in the lattice IR mode behavior, as observed for the natural phases and the H 2O-free phases. The standard entropy at 298 K for armenite is S° = 795.7 ± 6.2 J/mol K and its dehydrated analog is S° = 737.0 ± 6.2 J/mol K. For epididymite S° = 425.7 ± 4.1 J/mol K was obtained and its dehydrated analog has S° = 372.5 ± 5.0 J/mol K. The heat capacity and entropy of dehydration at 298 K are Δ C p rxn = 3.4 J/mol K and Δ S rxn = 319.1 J/mol K and Δ C p rxn = −14.3 J/mol K and Δ S rxn = 135.7 J/mol K for armenite and epididymite, respectively. The H 2O molecules in both phases appear to be ordered. They are held in place via an ion–dipole interaction between the H 2O molecule and a Ca cation in the case of armenite and a Na cation in epididymite and through hydrogen-bonding between the H 2O molecule and oxygen atoms of the respective silicate frameworks. Of the three different H 2O phases ice, liquid water and steam, the C p behavior of confined H 2O in both armenite and epididymite is most similar to that of ice, but there are differences between the two silicates and from the C p behavior of ice. Hydrogen-bonding behavior and its relation to the entropy of confined H 2O at 298 K is analyzed for various microporous silicates. The entropy of confined H 2O at 298 K in various silicates increases approximately linearly with increasing average wavenumber of the OH-stretching vibrations. The interpretation is that decreased hydrogen-bonding strength between a H 2O molecule and the silicate framework, as well as weak ion–dipole interactions, results in increased entropy of H 2O. This results in increased amplitudes of external H 2O vibrations, especially translations of the molecule, and they contribute strongly to the entropy of confined H 2O at T < 298 K.