Pyrolysis of tert-butanol (2.77% tert-butanol in argon) in a laminar plug flow reactor was studied at low pressure and a temperature range of 950-1850 K. More than 20 pyrolysis species were identified by using synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS); and their mole fraction profiles versus the pyrolysis temperature were evaluated. A kinetic model including 101 species and 511 reactions was developed and validated by both the pyrolysis data and recently reported rich premixed flame data (Combustion and Flame 2011; 158:2-15). Reaction flux analysis demonstrates that the main decomposition reaction sequence of tert-butanol in both pyrolysis and rich flame is tC(4)H(9)OH/IC4H8OH -> C4H8 -> C4H7 -> aC(3)H(4) -> pC(3)H(4) -> C2H2. The most remarkable difference is that the H2O elimination reaction is the dominant primary decomposition pathway of tert-butanol in the pyrolysis, while H-abstraction reactions control the primary decomposition of tert-butanol in the rich flame. (C) 2011 Elsevier Ltd. All rights reserved.