Clusters containing a phenylethylamine (PEA) or amphetamine (AMP) molecule and a solvent species such as Ar, CH4, CF3H, CO2, H2O, and other small molecules are formed in a supersonic jet expansion. Spectral studies of the solvation and related chemistry of PEA and AMP are pursued by using both fluorescence and mass spectroscopy techniques. To help analyze the experimental results, ab initio and atom-atom Lennard-Jones-Coulomb (LJC) potential calculations are employed to calculate cluster geometries and binding energies. The LJC potential parameters for the 10-12 hydrogen-bonding potentials have been reevaluated on the basis of new ab initio partial atomic charge values and new experimental binding energies and geometries. The observed dependence of the relative spectral intensities of PEA and AMP conformers and their clusters on the cooling conditions (backing pressure and coolants employed) suggests that these species undergo population redistribution in the cooling and clustering process. The amount of excess energy (binding energy) available to the forming cluster plays a major role in the conformational conversion of PEA and AMP during cluster formation. If strong interactions (hydrogen bonding) exist between the solute and the solvent, such conversion/ redistribution processes occur among all conformers and their clusters. The conversion/redistribution process is restricted within the anti or gauche conformer sets and their clusters for weakly interacting solute/solvent pairs. All PEA and AMP clusters studied experience complete fragmentation upon ionization. The observed gradual dependence of photo ion intensity on the ionization laser energy suggests a significant change in geometry for both PEA and AMP, as well as their clusters, upon ionization. Consequently the high vertical ionization energy leads to an excess energy in the vibrational modes of the ions, causing fragmentation of the clusters. The clusters can fragment along two different general paths: (1) simple loss of the solvent molecules and (2) breaking the alpha-beta carbon bond of PEA or AMP, with additional loss of solvent molecules in some cases. Those clusters with weaker solute/solvent binding tend to fragment through solvent loss, while those forming hydrogen bonds tend to favor the alpha-beta carbon bond cleavage. Reactions are observed for PEA and AMP with NO. NO can completely quench PEA and AMP monomer spectra. The reaction products include C6H5CH=CH2 and C6H5NH2 for PEA and C6H5CH=CHCH3 and C6H5NH2 for AMP.