Pellets are solid biofuels with a combustion efficiency of 85−90%, low CO2 emissions and costs, great comfort and versatility. However, the ash generated during combustion can present sintering and fusibility, decreasing boiler efficiency and potentially malfunctioning. Ash composition indexes can be useful to predict observed ash sintering and fusion but require further analysis for a variety of feedstocks. The objective of this work was to determine the effect of the mineral composition of pellet ash from 15 biomasses of forest and agro-industrial sources on observed pellet ash slagging using a laboratory test. The chemical composition of pellets and the indexes B, NaK/B, SiP/CaMg and SiPNaK/CaMg at 550 and 1000 °C were determined. Pearson correlation tests were also performed between cumulative percentages of slag at different sieve sizes. The concentrations of CaO ranged from 4.49 to 65.95%, MgO varied from 1.99 to 17.61%, and the SiO2 concentration was between 16.11 and 28.24% and 2.19−56.75% at 550 and 1000 °C, respectively. Pellets of forest origin presented a low risk of slag formation, while those from agro-industrial sources showed a high risk of slag formation. The index SiPNaK/CaMg showed the highest correlation (R2 > 0.75) to observed slagging using the BioSlag test.