Amplified spontaneous emission (ASE) from single rotational levels of Rydberg states, E(2) Sigma(+)(upsilon = 1), D-2 Sigma(+)(upsilon = 5), and F2 Delta(upsilon = 0), as well as valence states, L(2) Pi(upsilon = 2) and B-2 Pi(upsilon = 21), of NO molecules has been investigated. These states were populated through optical-optical double resonance excitation via the A(2) Sigma(+)-(upsilon’ = 0 and 1) states. ASE excitation spectra exhibited an excellent signal-to-noise ratio, demonstrating a high potential of the laser induced ASE (LIASE) technique as a novel spectroscopic technique for the study of excited states of small molecules. The rotational structure in dispersed ASE spectra have been fully resolved, which resulted in detailed information on the radiative ASE relaxation processes down to the A(2) Sigma(+) state.