The quantification of elemental sulfur (S0) is an important part of monitoring and controlling sulfur-involving processes. Existing methods of S0 detection either require significant time or involve the use of toxic chemicals. We have developed and validated a new method to determine S0 in environmental samples using calorimeter-ion chromatography (IC), in which S0 is fully oxidized to sulfur trioxide (SO3) with pure oxygen at 20 atm in a calorimeter. The resulting SO3 is then absorbed by a sodium bicarbonate (NaHCO3) solution and analyzed using IC. To verify this method, standard samples with various sulfur contents (5-200 mg S), possible interfering substances (SO42-, SO32-, S2O32- and S2-), and mixed environmental samples were tested and compared. The high correlation of R2 = 0.999 between the examined and theoretical values was obtained with a high recovery rate of ≥95% and a low relative standard deviation (RSD) of ≤1%. Samples containing at least 25 mg of S0 were accurately measured (recovery error < 5%). Thiosulfate was identified as the main interfering substance, and pretreatment was needed to eliminate it. This new method is more efficient, cost-effective, easier to operate, and more secure and accurate than existing methods.