© the Owner Societies 2017. Two sets of experiments were performed to unravel the high-temperature pyrolysis of tricyclo[5.2.1.02,6] decane (JP-10) exploiting high-temperature reactors over a temperature range of 1100 K to 1600 K, Advanced Light Source (ALS), and 927 K to 1083 K, National Synchrotron Radiation Laboratory (NSRL), with residence times of a few tens of microseconds (ALS) to typically 144 ms (NSRL). The products were identified in situ in supersonic molecular beams via single photon vacuum ultraviolet (VUV) photoionization coupled with mass spectroscopic detection in a reflectron time-of-flight mass spectrometer (ReTOF). These studies were designed to probe the initial (ALS) and also higher order reaction products (NSRL) formed in the decomposition of JP-10-including radicals and thermally labile closed-shell species. Altogether 43 products were detected and quantified including C1-C4 alkenes, dienes, C3-C4 cumulenes, alkynes, eneynes, diynes, cycloalkenes, cyclo-dienes, aromatic molecules, and most importantly, radicals such as ethyl, allyl, and methyl produced at shorter residence times. At longer residence times, the predominant fragments were molecular hydrogen (H2), ethylene (C2H4), propene (C3H6), cyclopentadiene (C5H6), cyclopentene (C5H8), fulvene (C6H6), and benzene (C6H6). Accompanied by electronic structure calculations, the initial JP-10 decomposition via C-H bond cleavages resulting in the formation of the initial six C10H15radicals was found to explain the formation of all products detected in both sets of experiments. These radicals are not stable under the experimental conditions and further decompose via C-C bond β-scission processes. These pathways result in ring opening in the initial tricyclic carbon skeletons of JP-10. Intermediates accessed after the first β-scission can further isomerize or dissociate. Complex PAH products in the NRLS experiment (naphthalene, acenaphthylene, biphenyl) are likely formed via molecular growth reactions at elevated residence times.