The fluorescence spectra of the intramolecular electron-transfer compound, N-(1-pyrenylmethyl)-N-methyl-4-methoxyniline (Py-Am), have been studied at different pressures. There are three emitting species in the excited molecules of Py-Am for the neat sample, local excited state of pyrene group for monomer emission, intermolecular exciplex, and intramolecular exciplex. The exciplexes are difficult to characterize at ambient pressure. Pressure tuning for the electronic states shows its powerful ability to distinguish the different properties of the states. Under the effect of pressure, the intermolecular and intramolecular exciplexes are observed clearly with different tendencies to change their emission intensity at significantly different wavelengths.