Vibrationally mediated photodissociation action spectroscopy provides rotation-vibration spectra of jet-cooled ammonia in the 2.3 μm and 3.0 μm regions by detecting the emission of electronically excited NH2(Ã 2A1) produced by the photodissociation of the vibrationally excited molecules. Vibrational excitation changes the relative photofragmentation yield of NH2(Ã 2A1) markedly. Isoenergetic photolysis of ammonia molecules with one quantum of antisymmetric N–H stretching excitation (ν3) or two quanta of bend (2ν4) yields three times more excited state NH2(Ã 2A1) than photolysis of NH3 with a quantum of symmetric N–H stretch excitation (ν1). By contrast, the relative yield is insensitive to initial vibrational excitation of the combination bands ν1+ν2 and ν2+ν3 that contain the umbrella (inversion) motion ν2. The vibrational mode dependence of the NH2(Ã 2A1) photofragment yield arises from either enhanced Franck–Condon factors for electronic excitation or from an increased probability for the competing nonadiabatic dissociation to form the ground state NH2(X̃ 2B1) product.