Four colorless tourmalines of the liddicoatite-elbaite series from pegmatites from Anjanabonoina, Madagascar, have been characterized by crystal-structure determination and by chemical analyses. Optimized formulae range from X(Ca0.57Na0.29□0.14) Y(Al1.41Li1.33Mn2+0.07□0.19)Z Al6T(Si5.86B0.14)O18 (BO3)3V (OH)3.00W[F0.76(OH)0.24] [a = 15.8322(3), c = 7.1034(3) Å] to X(Na0.46Ca0.30□0.24) Y(Al1.82Li0.89Fe2+0.01 Mn2+0.01□0.27) ZAl6T(Si5.56B0.44)O18 (BO3)3V(OH)3.00W[(OH)0.50F0.50] [a = 15.8095(9), c = 7.0941(8) Å] (R = 1.3–1.7%). There is a high negative correlation (r2 = 0.984) between the <T-O> bond-lengths (~1.618–1.614 Å) and the amount of IVB (from the optimized formulae). Similar to the olenites (from Koralpe, Austria) the liddicoatite-elbaite samples show a positive correlation between the Al occupancy at the Y site and IVB (r2 = 0.988). Short-range order configurations show that the presence of IVB is coupled with the occupancy of (Al2Li) and (Al2□) at the Y site. The structural formulae of the Al-rich tourmalines from Anjanabonoina, Madagascar, show ~ □0.2 (vacancies) on the Y site. We believe that short-range order configurations with Y(Al2□) are responsible for these vacancies. Hence, an oft-used calculation of the Li content by difference on the Y site may be problematic for Al-rich tourmalines (olenite, elbaite, rossmanite). Fourier transform infrared (FTIR) spectra were recorded from the most IVB-rich tourmaline sample. The bands around 5195 and 5380 cm−1 can be assigned to H2O. Because these bands still could be observed in FTIR spectra at temperatures from −150 to +600 °C, it seems unlikely that they result from H2O in fluid inclusions. Interestingly, another FTIR spectrum from a dravite in which the X site is filled completely with Na, does not show bands at ~5200 and ~5400 cm−1. Although not definitive, the resulting spectra are consistent with small amounts of H2O at the X site of the elbaite. The rare-earth element (REE) pattern of the B-rich elbaite (∑REE: ~150 ppm) demonstrates that this sample is strongly enriched in LREEs compared to HREEs and exhibits a negative Eu anomaly. This sample shows the strongest enrichment of LREEs and a high LaN/YbN ratio of ~351, which seems to confirm an important role of the fractional crystallization process.