Abstract: Mössbauer spectra of iron-bearing tourmaline, obtained at different temperatures, show the existence of thermally-activated charge delocalization among clusters of iron atoms situated in the Y and Z octahedra of the tourmaline structure. The temperature dependence indicates an unusually high activation energy for the delocalization process which suggests that the process takes place between crystallographically non-equivalent sites. Annealing of the tourmaline in hydrogen is observed to inhibit the delocalization process, thus localizing the electron into the Z-site.