Conformational isomers of alkanethiols are isolated in the molecular beam, and the conformer-specific ionization dynamics have been investigated using vacuum ultraviolet mass-analyzed threshold ionization (MATI) spectroscopy. Only a single conformer of ethanethiol is observed to give the adiabatic ionization potential (IP) of 9.2922 +/- 0.0007 eV for the gauche conformer. For isopropanethiol, IP is found to be 9.1426 +/- 0.0006 for the trans conformer and 9.1559 +/-0.0006 eV for the gauche conformer. Only two major conformational isomers are identified for 1-propanethiol, giving an IP of 9.1952 +/-0.0006 for the trans-gauche conformer and 9.2008 +/- 0.0006 eV for the gauche-gauche conformer. The tert-butanethiol, as expected, has a single conformer with an IP of 9.0294 +/- 0.0006 eV. For 1-butanethiol, there are a number of conformers, and the assignment of the MATI bands to each conformer turns out to be nontrivial. The spectral simulation using the Franck-Condon analysis based on the density functional theory (DFT) calculations has been used for the identification of each conformational isomer in the MATI spectrum. Each conformer undergoes its unique structural change upon ionization, as revealed in the vibration resolved MATI spectrum, providing the powerful method for the spectral identification of a specific conformational isomer. The conformer specificity in the ionization-driven structural change reflects the role of the electron of the highest occupied molecular orbital (HOMO) in the conformational preference.