The binary diagram for pyrimidine:water mixtures has been determined by differential scanning calorimetry, in situ single-crystal, and powder X-ray diffraction experiments. The eutectic point has been located near the 1:4 n/n ratio at 234.5 K. The eutectic and nearly eutectic mixtures easily vitrify, and the vitrification could be kinetically induced for 1:3 n/n mixtures, too. Depending on the cooling rate, the 1:4 mixture freezes in the glass state, as a conglomerate of the glass and crystalline phases, or as the eutectic mixture of pyrimidine phase I and hexagonal ice I-h. When heated above 160 K, the glass phase transforms to a novel crystalline phase, tentatively identified as a pyrimidine hydrate, which in turn at ca. 200-210 K transforms into a eutectic mixture of pyrimidine phase I and hexagonal ice I-h. The pyrimidine-water binary diagram and novel crystalline and amorphous phases are relevant to the thermodynamic behavior of hydrophilic pyrimidine and its natural and synthetic derivatives in humid environments. The presently determined binary diagram can be straightforwardly applied for assessing the contents of water in highly hygroscopic pyrimidine samples.