Fire and explosion hazards pose significant safety concerns in the processing and storage of biomass particles, warranting the safe utilization of these particles. This study employed scanning electron microscopy, thermogravimetric analysis, and cone calorimetry to investigate the thermal hazards and toxicity of raw biomass particles from four prevalent agricultural crops in China: rice, sorghum, corn, and reed. Among the samples, corn exhibited the highest heat output of 8006.82 J/g throughout the thermal decomposition process. The quantitative evaluation of critical heat flux, heat release rate intensity, fire growth rate index (FIGRA), post-ignition fire acceleration (PIFA) and flashover potential (X) revealed a substantial fire risk inherent to all the examined straw samples. Notably, corn displayed the lowest FIGRA value of 8.30 kW/m2 s, while rice demonstrated the minimum PIFA value of 16.11 kW/m2 s. Moreover, the X values for all four biomass particle types exceeded 10 under varying external heat flux levels, indicating their high propensity for fire hazards. Analysis of CO and CO2 emissions during combustion showed all four biomass samples exhibited high concentrations throughout, from the initial stages to the end. The present study offers crucial insights for formulating comprehensive fire safety guidelines tailored to the storage and processing of biomass particles.