The stratovolcano Mt. Pelée, Martinique, exhibits eruptive styles ranging from dome formation to sustained, highly violent explosive activity. Historical eruptions have produced lava domes and pyroclastic density currents, collectively termed Peléan activity. In pre-colonial times, several Plinian eruptions took place. Here, we explore physical controls on the proportions of fine particles produced—i.e., the fragmentation efficiency—during primary fragmentation. Samples were collected from ignimbrites from the 1929–1932 and 1902–1905 Peléan eruptions and the P1 (1300 CE), P2 (280 CE), and P3 (79 CE) Plinian eruptions. All samples are andesitic in bulk composition and contain a rhyolitic groundmass glass. The Peléan materials are more crystalline and less porous than their Plinian counterparts, a consequence of more extensive outgassing during dome formation. Representative blocks were cored and experimentally fragmented following rapid decompression (> 1 GPa·s−1 from initial pressure between 5 and 20 MPa). Dry sieving allowed for determining grain size distributions, from which the fractal dimensions, Df, were calculated as a quantification of fragmentation efficiency. Our results indicate different behaviors for Peléan and Plinian samples. While fragmentation efficiency is positively correlated with applied potential energy for Peléan samples, this relationship is not observed for the Plinian samples, possibly due to syn-fragmentation gas escape above a certain porosity. The rapid decompression experiments were designed to minimize secondary fragmentation by shear along the walls or impact while preserving the entirety of produced materials. Thus, our experimental grainsize data are physically linked to sample textures and overpressure. By comparison with natural pyroclastic products—commonly incompletely preserved—we can approach quantitatively constraining the energetic conditions underlying individual eruptions.