The multiphoton (one-colour) excitation spectrum of jet-cooled 4-H-1-benzopyrane-4-thione (BPT) is investigated in the wavelength region from 570 to 640 nm. The emission from BPT after multiphoton excitation was detected in two wide ranges in the blue (approximate to 400-500 nm) and the near UV (approximate to 250-400 nm). Resonance-enhanced excitation via the first excited triplet state S-0-->T-1-->Psi(S,T)(') and the first excited singlet state S-0-->S-1-->Psi(S,T)('') is observed. The time dependence of the luminescence shows two components: (i) a fast decay component (tau(f) < 50 ns), whose main part is assigned to S-2-->S-0 fluorescence after two-photon excitation; (ii) a slow component (tau(f) approximate to 2 mu s) which may be attributed to the emission from a photofragment (CS*), efficiently created in a metastable triplet state by a four-photon absorption.The multiphoton (one-colour) excitation spectrum of jet-cooled 4-H-1-benzopyrane-4-thione (BPT) is investigated in the wavelength region from 570 to 640 nm. The emission from BPT after multiphoton excitation was detected in two wide ranges in the blue (approximate to 400-500 nm) and the near UV (approximate to 250-400 nm). Resonance-enhanced excitation via the first excited triplet state S-0-->T-1-->Psi(S,T)(') and the first excited singlet state S-0-->S-1-->Psi(S,T)('') is observed. The time dependence of the luminescence shows two components: (i) a fast decay component (tau(f) < 50 ns), whose main part is assigned to S-2-->S-0 fluorescence after two-photon excitation; (ii) a slow component (tau(f) approximate to 2 mu s) which may be attributed to the emission from a photofragment (CS*), efficiently created in a metastable triplet state by a four-photon absorption.