An optical and two-photon resonant multiphoton ionization and photoacoustic spectroscopic investigation of the second transition region of norbornadiene was conducted on static and jet-cooled samples. Transitions to both the 3s Rydberg and the NV2 valence states were observed. The substructure of the 3s Rydberg ← X̃ transition was deduced to arise from fundamentals, overtones, and combinations of a1, v4, v8, v10, and v12 and overtones and combinations of a2, v18, and v20 vibrational modes. Displacements from the ground-state equilibrium geometry were determined for the a1 modes. The 3s Rydberg state was shown to decay rapidly to the higher energy NV2 valence state via the v20 vibrational mode when energetically possible. The diffuse substructure of the NV2 transition was deduced to arise from V7, an ethylenic CH bending mode. Comparisons were made between results obtained here and those observed for similar molecules, observed for other states of this molecule, and calculated for these states of norbornadiene.