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The mitigation of industrial fire-induced losses is of growing importance. This study reports an experimental investigation of the combustion inhibition efficiency of calcium halides (CaX2), which are potential candidates for phosphorus-free fire-extinguishing agents. The results of the analysis, which used CaX2 (X = F, Cl, Br, and I) in suppression experiments, revealed that CaCl2, CaBr2, and CaI2 are more effective by factors of ca. 2.4, 4.5, and 4.6, respectively, than ammonium dihydrogen phosphate (ADP), which is an active component of conventional powder fire-extinguishing agents. The inhibition ability ranking of the tested CaX2 is CaI2 > CaBr2 > CaCl2 > CaF2. Kinetic analyses demonstrated that CaCl2, CaBr2, and CaI2 do not hinder the pyrolysis of cellulose although they hamper the combustion of residual char. CaX2 with lower lattice energies was confirmed to exhibit the strongest combustion inhibition abilities.