We present the results of photoelectron velocity-map imaging experiments for the photodetachment of small negatively charged ammonia solvated Bi-n and Pb-n (n = 1, 2) clusters at 527 nm. The vertical detachment energies of the observed multiple electronic bands and their respective anisotropy parameters for the solvated Bi and Pb anions and clusters derived from the photoelectron images are reported. The electronic bands of Bi(NH3)(n=1,2) are distinct from the Bi metal ion in exhibiting a perpendicular distribution whereas the electronic bands in Pb(NH3)(n=1,2), unlike the Pb anion, show an isotropic distribution with respect to the laser polarization. Density-functional theory calculations with a generalized gradient approximation for the exchange correlation potential were performed on these clusters to determine their atomic and electronic structures. Calculated geometries show a dramatic change between anionic and neutral ammonia solvated Bi and Pb species. Anionic clusters exhibit van der Waals interactions between the hydrogen atoms of ammonia and the metal core, where it was determined that the negative charge is localized. Neutral clusters, on the other hand, present a covalent bond between the nitrogen atom of ammonia and the metal core. Calculated binding energies show an enhancement in the bonding of the (NH3)(2) dimer in the presence of the anionic Bi-1.2(-) and Pb-1,2(-) metal ions. This is rationalized by the electrostatic interaction between the negative charged metal core and the hydrogen atoms of the ammonia molecule.