The photophysics of 1-aminonaphthalene (1-napthylamine, AMN) has been investigated on the basis of a constructive experimental-theoretical interplay derived from time-resolved measurements and high-level quantum-chemical ab initio CASPT2//CASSCF calculations. Transient ionization signals at femtosecond resolution were collected for AMN cold isolated molecules following excitation from the vibrationless ground level to a number of vibrational states (within the pump resolution) in the lowest accessible excited state and further multiphoton ionization probing at 500, 800, and 1300 nm. Theory predicts two pipi* states, (1)L(b) and (1)L(a), as the lowest singlet electronic excitations, with adiabatic transitions from S(0) at 3.50 and 3.69 eV, respectively. Since the associated oscillator strength for the lowest transition is exceedingly small, the (1)L(b) state is not expected to become populated significantly and the (1)L(a) state appears as the main protagonist of the AMN photophysics. Though calculations foresee a surface crossing between (1)L(a) and the lower (1)L(b) states, no dynamical signature of it is observed in the time-dependent measurements. In the relaxation of (1)L(a), the radiant emission competes with the intersystem crossing and internal conversion channels. The rates of these mechanisms have been determined at different excitation energies. The internal conversion is mediated by a (1)L(a)/S(0) conical intersection located 0.7 eV above the (1)L(a) minimum. The relaxation of a higher-lying singlet excited state, observed above 40 000 cm(-1) (4.96 eV) and calculated at 5.18 eV, has been also explored.