Organic peroxides are widely used in the chemical industry as initiators or curing agents for polymerization reactions. However, the use of peroxides presents an intrinsic hazard due to the presence of the highly unstable peroxy group which causes peroxides readily decompose. In present study, the thermal hazards of a selected organic peroxide, the benzoyl peroxide (BPO), were experimentally investigated by using adiabatic calorimetry. On the basis of experimental results, the thermal hazard parameters under adiabatic conditions were estimated. Preliminary data with respect to decomposition onset temperatures and decomposition heat were obtained by simultaneous TG-DSC-FTIR analysis. A Phi-Tec II adiabatic calorimeter was used to study the thermal decomposition of the selected peroxide. The experimental data obtained allowed the assessment of thermokinetic parameters. Decomposition products formed during the experimental runs were sampled and characterized by FTIR and gas chromatographic techniques. The results obtained in the present investigation could be useful for the adoption of inherently safer design in the manufacturing, handling, storage, and disposal of organic peroxides.