Photodissociative experiments were performed on Cu+-C5H5N and Ag+-C5H5N complexes in the gas phase; The dissociative ligand-to-metal charge-transfer fragments, pyridine(+), were observed for both complexes. Photodissociation spectra were recorded as a function of laser wavelength. Two continuous, structureless bands were investigated in each complex. Because of the low-energy D-2 state of the Cu atom, the Cu+-pyridine dissociative process is more complicated. Several possible mechanisms for this process have been discussed. The binding energies were determined experimentally to be 65.5 and 45.2 kcal/mol for Cu+-pyridine and Ag+-pyridine, respectively. M+-C5H5N (M = Cu or Ag) complexes also were studied theoretically using the HF, MP2, and B3LYP methods. All complexes under study show C-2 nu symmetry. The binding energies predicted from the theoretical calculations were less than the experimental values, which were derived from the onset of the charge-transfer appearance combined with the LP (ionization potential). The complexes containing Cu+ and Ag+ are characterized predominantly by electrostatic interactions.