Laser-desorption jet-cooling has been applied in combination with mass-selective gas-phase spectroscopic techniques to study the structure and low-frequency vibrations of diphenylamine (DPA). Two-color (1 + 1’) resonance-enhanced multiphoton ionization has been used to measure the vibrationally resolved excitation spectrum of the S-1<--S-0 transition in the 305-309 nm region. Ion-dip measurements have been performed to determine the vibrational structure in the electronic ground stale. The electronic spectra of DPA are dominated by long progressions in low-frequency vibrations involving the motion of the phenyl rings as a whole. For the interpretation of the experimental data ab initio calculations have been performed at the Hartree-Fock level for the S-0-state and using single-excitation configuration interaction for the S-1-state. The DPA molecule is found to change from a pyramidal geometry around the N-atom with unequal torsional angles of the phenyl groups in the S-0-state to a planar geometry with equal torsional angles in the S-1-state. The two most prominent vibrational motions are the in-phase wagging and the in-phase torsion of the phenyl rings. In addition, the resonance-enhanced multiphoton ionization spectra of the S-1<--S-0 transition in the DPA-Ar, DPA-Kr, and DPA-Xe van der Weals complexes have been measured. From these spectra it is inferred that there is a coupling between the van der Waals modes and the low-frequency intra-molecular modes of DPA.