Mechanochemistry is emerging as a powerful solvent-free approach to chemical synthesis, having been applied to metal oxides, pharmaceutical materials, organic compounds and to a lesser extent, coordination complex synthesis. Notably, examples of applications of mechanochemical methodologies in the synthesis of main-group compounds are few and far between. Herein, we demonstrate that ball milling enabled the solvent-free synthesis of a range of phosphazane frameworks with a broad substrate scope, yielding seven new acyclic and macrocyclic species. The strength of this methodology is highlighted by a fast, selective and high-conversion product generation from poorly soluble starting materials, thereby demonstrating mechanochemistry as a real alternative to solution-based methods in synthetic main-group chemistry. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim