Tourmaline, the first pyroelectric material discovered, is also a promising borosilicate material with non-linear optical and luminescence properties, high thermal stability, high hardness and variable chemical composition. The structural nature of pyroelectricity in tourmaline is a subject of scientific debate since it requires precise structural studies and measurements at elevated temperatures. Here, an in situ high temperature single-crystal and powder X-ray diffraction studies (up to ~1000 ◦C) and the direct pyroelectric measurements (up to ~200
◦C) of synthetic Ni, Al-rich tourmaline were performed. The pyroelectric coefficient was calculated from the structural data. The results demonstrate that polyhedra XO9, YO6 and ZO6 exert the greatest influence on the pyroelectric effect. The pyroelectric coefficient of tourmaline is practically independent of boron-oxygen triangles and silicon-oxygen tetrahedra. The primary pyroelectric coefficient of tourmalines could be calculated from single crystal structural data. This study contributes to the synthesis of tourmalines with the required pyroelectric properties and may be used for the study of the nature and properties of other pyroelectric materials.