The development of an analytical method for quantification of thermally labile organic hydroperoxides in jet fuel via reaction with triphenylphosphine (TPP) is explored. The primary goal of this work is to devise a technique for hydroperoxide detection in jet fuel, for use in fuel oxidation studies, that will use only small sample volumes (< 1 mL), have a low detection limit (< 0.02 mM), have a broad dynamic range, and be fast, reproducible, and accurate. The reported technique uses the reaction of TPP with hydroperoxides to form triphenylphosphine oxide (TPPO) and the subsequent alcohol, which proceeds rapidly in jet fuel (less than 1 min) at ambient conditions. Elemental sulfur was used prior to analysis as a novel means to prevent the oxidation of TPP during chromatographic analysis by converting excess TPP into triphenylphosphine sulfide (TPPS) via another rapid, ambient condition reaction. Gas chromatographic (GC) analysis with flame ionization detection (FID) was used to quantify the resulting TPPO and TPPS, and the relative TPPO peak area was observed to be proportional to the hydroperoxide concentration. The production of TPPO by an interfering reaction was observed; however, TPPO produced via this reaction occurred predominantly in thermally stressed fuels, when large amounts of excess TPP were used. By limiting the amount of excess TPP used during the analysis we were able to control this interfering source of TPPO. The accuracy of the reported TPP method compares favorably with ASTM D6447. Finally, we report that the resulting method requires a small sample volume (0.5 mL), has a very low detection limit (0.002 mM), has a wide dynamic range, and is accurate and reproducible.