The microsolvation and photophysics of 3-amino-1,2,4-triazole (3AT) after excitation to the light-absorbing S-2(n pi*) state were studied by using resonance Raman spectroscopy and single component artificial force-induced reaction (SC-AFIR) in a global reaction route mapping (GRRM) strategy. The vibrational spectra were assigned on the basis of experimental data and density functional theory (DFT) calculations. The resonance Raman spectra of 3AT were measured to probe the excited state structural dynamics in the Franck-Condon region. The conformations of 3AT(CH3CN)(1), 3AT(CH3OH)(2), and 3AT(H2O)(2) clusters were determined by combining vibrational spectrum experiments and B3LYP/6-311++G(d,p) computations. DFT calculations were carried out to obtain the minimal excitation energies of the lower-lying singlet excited states, and the curve-crossing points. It was revealed that the short-time structural dynamics of 3AT were dominated by the N-N stretching coordinates. An excited state decay mechanism is proposed: 3AT is initially excited to the S-2(n pi*) state, then the conical intersection (CI) of the S-2(n pi*)/S-1(pi pi*) potential energy surfaces is crossed, and 3AT then decays to the lower solvent-dependent excited state S-1(pi pi*). It subsequently returns to the S-0 state, accompanied by a large Stokes fluorescence shift, which was interpreted as the stabilized S-1(pi pi*) excited state bonding to several water molecules via intermolecular hydrogen bonding.