Tourmaline grains extrcted from rocks within three ultrahigh-pressure (UHP) metamorphic localities have been subjected to a structurally and chemically detailed analysis to test for any systematic behavior related to temperature and pressure. Dravite from Parigi, Dora Maira, Western Alps (peak P-T conditions ~3.7 GPa, 750 °C), has a structural formula of X(Na0.90Ca0.05K0.01□0.04)Y(Mg1.78Al0.99Fe2+0.12Ti4+0.03□0.08)Z(Al5.10Mg0.90)(BO3)3TSi6.00O18V(OH)3W[(OH)0.72F0.28]. Dravite from Lago di Cignana, Western Alps, Italy (~2.7–2.9 GPa, 600–630 °C), has a formula of X(Na0.84Ca0.09K0.01□0.06)Y(Mg1.64Al0.79Fe2+0.48Mn2+0.06Ti4+0.02Ni0.02Zn0.01)Z(Al5.00Mg1.00)(BO3)3T(Si5.98Al0.02)O18V(OH)3W[(OH)0.65F0.35]. “Oxy-schorl” from the Saxonian Erzgebirge, Germany (≥4.5 GPa, 1000 °C), most likely formed during exhumation at >2.9 GPa, 870 °C, has a formula of X(Na0.86Ca0.02K0.02□0.10)Y(Al1.63Fe2+1.23Ti4+0.11Mg0.03Zn0.01) Z(Al5.05Mg0.95)(BO3)3T(Si5.96Al0.04)O18V(OH)3W[O0.81F0.10(OH)0.09]. There is no structural evidence for significant substitution of Si by Al or B in the UHP tourmaline (<T-O> distances ~1.620 Å), even in high-temperature tourmaline from the Erzgebirge. This is in contrast to high-T–low-P tourmaline, which typically has significant amounts of Al. There is an excellent positive correlation (r2 = 1.00) between total Al (i.e., YAl + ZAl) and the determined temperature conditions of tourmaline formation from the different localities. Additionally, there is a negative correlation (r2 = 0.97) between F content and the temperature conditions of UHP tourmaline formation and between F and YAl content (r2 = 1.00) that is best explained by the exchange vector YAlO(R2+F)−1. This is consistent with the W site (occupied either by F, O, or OH), being part of the YO6-polyhedron. Hence, the observed Al-Mg disorder between the Y and Z sites is possibly indirectly dependent on the crystallization temperature.