We demonstrate a new spectroscopic method for studying electronic transitions in molecules with extremely broad range of angular momentum. We employ an optical centrifuge to create narrow rotational wave packets in the ground electronic state of $^{16}$O$_2$. Using the technique of resonance-enhanced multi-photon ionization, we record the spectrum of multiple ro-vibrational transitions between $X^3Σ_{g}^{-}$ and $C^3Π_{g}$ electronic manifolds of oxygen. Direct control of rotational excitation, extending to rotational quantum numbers as high as $N\gtrsim 120$, enables us to interpret the complex structure of rotational spectra of $C^3Π_{g}$ beyond thermally accessible levels.

5 pages, 6 figures