Mass‐selective ground‐state vibrational spectra of jet‐cooled carbazole⋅R (R=Ne, Ar, Kr, and Xe) van der Waals complexes were obtained by populating ground‐state intra‐ and intermolecular levels via stimulated emission pumping, followed by time delayed resonant two‐photon ionization of the vibrationally hot complex. By tuning the dump laser frequency, S0 state vibrational modes were accessed from ≊200 cm−1 up to the dissociation energy D0. Upon dumping to ground‐state levels above D0, efficient vibrational predissociation of the complexes occurred, allowing us to determine the S0 state van der Waals binding energies very accurately. The D0(S0) values are <214.5±0.5 cm−1 (R=Ne), 530.4±1.5 cm−1 (R=Ar), 687.9±4.0 cm−1 (R=Kr), and 890.8±1.6 cm−1 (R=Xe). In the S1 state, the corresponding binding energies are larger by 9% to 12%, being <222.9±1.0 cm−1, 576.3±1.6 cm−1, 756.4±4.5 cm−1, and 995.8±2.5 cm−1, respectively.