Laser induced fluorescence (LIF) and resonantly enhanced multiphoton ionization (REMPI) studies of van der Waals complexes of aniline and 4-aminobenzonitrile (4-ABN) with some polar solvents are reported. The 1+1 clusters of aniline with methanol, acetone, and water do not fluoresce. The REMPI spectrum of 1+1 cluster of aniline with methanol shows only a broad band, which indicates a large change in geometry between ground and excited states. For complexes of aniline with acetone or water, the 1+1 signals in the mass spectra are from the dissociation of larger clusters. The molecule 4-aminobenzonitrile forms fluorescent 1+1 clusters with methanol and acetonitrile which have emission spectra similar to that of uncomplexed 4-aminobenzonitrile. In the complexes, the broad background that appears in the emission spectrum occurs at lower excess energy. Solvatochromism studies of 4-fluorobenzonitrile (4-FBN), aniline, 4-ABN, 1-cyanonaphthalene (1-CNN), 1-aminonaphthalene (1-AMN), and 1-amino-4-cyanonaphthalene (p-AMCNN) are also reported. The solvatochromism study shows that those molecules giving rise to broad emission in the,,as phase (aniline, 4 4-ABN, 1-AMN, and p-AMCNN) have a large solvatochromic shift, implying that in solution their emitting excited states have larger dipole moments than those of the ground states. The molecules with sharp gas-phase spectra, 4-FBN and 1-CNN, have little or no solvatochromic shift in solution.