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Transition metal bis(arene) sandwich complexes may adopt eclipsed or staggered conformations due to the aromatic ring rotations about the metal-arene axis.$\mathrm{<mrow\; data-mjx-texclass="ORD">,</mrow>}$ In this study, the group VI (Cr, Mo, and W) metal bis(toluene) complexes are synthesized in a laser-ablation molecular beam source, and their rotational conformers are identified by pulsed-field-ionization zero-electron-kinetic-energy (ZEKE) spectroscopy. For Cr-bis(toluene), the ZEKE spectrum shows three distinctive vibrationless (0-0) transitions between the ground electronic states of the neutral and ionic complexes at 42739(5), 42745(5), and 42805(5) cm$\mathrm{<mrow\; data-mjx-texclass="ORD">-1</mrow>}$, corresponding to ionization energies of $180irc$, $60irc$/$120irc$, and $0irc$ rotamers. In addition, the spectrum exhibits metal-toluene bending (164, 180, 196, and 223 cm$\mathrm{<mrow\; data-mjx-texclass="ORD">-1</mrow>}$) and stretching (278 and 291 cm$\mathrm{<mrow\; data-mjx-texclass="ORD">-1</mrow>}$) frequencies of these rotamers. The ground electronic states of the $0irc$ and $180irc$ rotamers are $\mathrm{<mrow\; data-mjx-texclass="ORD">1</mrow>}$A$1$ (C) and $\mathrm{<mrow\; data-mjx-texclass="ORD">1</mrow>}$A (C) in the neutral form and $\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$A$1$ (C) and $\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$A (C) in the ionized form, respectively. For the $60irc$ and $120irc$ rotamers, the ground states of the neutral molecules are $\mathrm{<mrow\; data-mjx-texclass="ORD">1</mrow>}$A (C$2$), and those of the corresponding ions are $\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$A (C$2$). Through the variation of the molecular beam conditions, the eclipsed conformer ($0irc$) is determined to be more stable than the staggered ones ($180irc$, $120irc$, and $60irc$). Similarly, multiple conformers are identified for the Mo and W complexes.