The zeolite water arrangement in laumontite Ca3.85Na0.23K0.06Al7.96Si16.03O48·nH2O (n=16–18) and leonhardite (n=12–14.4) has been studied from1H and27Al-NMR data at temperatures of 200–390 K. Close agreement is found between NMR data obtained for samplesn=12 andn=18 and previous X-ray and neutron diffraction data. The H2O arrangement in the powder sample withn=14.4 and in a laumontite single crystal is represented by a combination of the H2O arrangements in samples withn=12 andn=18 with increased orientational H2O disordering. Concentration-type phase transitions are found in the single crystal and then=16 andn=18 samples at 226 and 230 K, and orientational-type phase transitions are found in the sample withn=14.4 at 230 K, and in the sample withn=18 at 293 K. The smooth transformations into an orientationally disordered glassy state arrangement of H2O in the zeolite channels is found in smaples withn=14.4, 16, and 18 at 300–330 and 305–315 K.