This study investigates the thermal decomposition of BP into B12P2, with a particular focus on the heterogeneous solid-gas mechanism involving BP powders synthesized via self-propagating high temperature reactions. Various techniques, including XRD, TGA, SEM, TEM, EELS and SAED, were combined to examine morphological and structural changes at different temperatures. The results reveal an ignition temperature for decomposition at 1120 °C, beyond which BP grains undergo fragmentation into smaller particles, accompanied by the release of phosphorous gases (P2(g), P4(g)). Additionally, Rietveld refinements on thermally treated powders facilitated the determination of advancement rate values of the decomposition reaction under different isothermal conditions. Based on these kinetic data obtained at 1300 °C, a one-process nucleation-growth model with instantaneous nucleation and anisotropic growth has be established. In particular, the law, which describes the process for a spherical grain with inward development and a reaction occurring at the internal interface as the step determining the rate, displayed a strong correlation coefficient, offering novel insights into the kinetic evolution of the BP to B12P2 conversion. These results contribute to a deeper understanding of the thermal decomposition process and its underlying elementary mechanisms.