Chromium-bearing tourmalines are rare. Chromium-rich tourmaline from the northwestern part of the Adirondack Mountains in the Adirondack Lowlands is among the most chromium-rich tourmalines found to date. The mineral, with \>21.0 wt. \% Cr₂O₃, is from the marble-hosted talc–tremolite–cummingtonite schist in the \#1 mine in Balmat, St. Lawrence County, New York. The atomic arrangement of the sample (a = 16.0242(3) \r A, c = 7.3002(2) \r A) was refined to R1 = 0.0139. The composition, from chemical analyses and optimization of the formula, is ^X(Ca_0.22Na_0.69K_0.01) ^Y(Cr³⁺_1.68Mg_0.80Ti_0.13V_0.06Mn_0.02Fe_0.02Li_0.29) ^Z(Al_3.11Cr³⁺_1.18Mg_1.70Fe_0.01) ^T(Si_5.93Al_0.07) B₃O₂₇ OH_3.99 F_0.01. There has been extensive debate over the ordering of Cr³⁺ between the tourmaline Y and Z octahedral sites. Recent work has suggested that, at low concentrations (\<~1.03 apfu), the substituent Cr³⁺ is ordered into the Y-site, whereas, at greater concentrations, the substituent is disordered over both octahedral sites. An analysis of nine recently published, high-precision structures of chromium-bearing tourmaline, in combination with the Adirondack tourmaline, suggests that structural changes to the Y-site at low concentrations of Cr³⁺ induce changes in the Z-site that make it more amenable to incorporation of the Cr³⁺ substituents by increasing \<Z–O\>. The bond lengths change to lower the bond-valence sum of Cr³⁺ in the Z-site of the chromium-dravite, making that site more amenable to the substituent. Calculations suggest that the Z-site begins to accept substituent Cr³⁺ when the bond valence sum of that ion in Z reduces to a value of ~3.36 valence units.