Vacuum ultraviolet (VUV) mass-analyzed threshold ionization (MATI) spectrum of supersonically cooled methylcyclohexane has been obtained to give the precise adiabatic ionization energy of 9.6958 +/- 0.0025 eV for the chair equatorial conformer. Vibrationally resolved MATI spectrum has been analyzed with the aid of density functional theory and Franck-Condon calculations. The MATI spectrum reflects the structural change upon ionization and its origin is discussed by inspecting the shapes of the valence orbitals involved in the ionization process. The spectroscopic implication of the structural interconversion above the certain energy level is discussed with theoretical calculations of molecular structures and energetics. (C) 2011 Elsevier B.V. All rights reserved.