The kinetics of pyrolysis of pyrrole dilute in argon have been studied in a single pulse shock tube, using capillary column GC, together with GC/MS and FTIR for product identification, over the temperature range 1200–1700 K, total pressures of 7.5–13.5 atm and nominal mixture compositions of pyrrole of 5000 and 700 ppm (nominal concentrations of 5 × 10−7 and 7 × 10−8 mol cm−3). Time‐resolved measurements of the rate of disappearance of pyrrole behind reflected shock waves have been made by absorption spectroscopy at 230 nm, corresponding to the lowest 1π* ← 1π transition of pyrrole at pressures of 20 atm and mixture compositions between 1000–2000 ppm pyrrole (1.7–3.0 × 10−7 mol cm−3) over the temperature range of 1300 to 1700 K. At the lower end of the studied temperature range, the isomers of pyrrole, allyl cyanide and cis‐ and trans‐crotononitrile, were the principal products, together with hydrogen cyanide and propyne/allene. At elevated temperatures, acetylene, acetonitrile, cyanoacetylene, and hydrogen became important products. The rate of overall disappearance of pyrrole, as measured by absorption spectrometry, was found to be first order in pyrrole concentration, with a rate constant kdis(pyrrole) = 1014.1±0.7 exp(−74.1 ± 3.0 kcal mol−1/RT) s−1 between 1350–1600 K and at a pressure of 20 atm. First order dependence of pyrrole decomposition and major product formation was also observed in the single pulse experiments over the range of mixture compositions studied. A 75‐step reaction model is presented and shown to substantially fit the observed temperature profiles of the major product species and the reactant profile. In the model the initiation reaction is postulated to be the reversible formation of pyrrolenine, (2H‐pyrrole). Pyrrolenine can undergo ring scission at the C2N bond forming a biradical which can rearrange to form allyl cyanide and crotononitrile or undergo decomposition to form HCN and C3H4 or acetylene and a precursor of acetonitrile. The model predicts an overall rate of disappearance of pyrrole in agreement with the experimental measurements.