beta-Enamino ketone (I) is experimentally shown to have a strong red shifted absorption maximum in its electronic spectrum in polar solvents and theoretically predicted to have high quadratic hyperpolarizability. Electron releasing and withdrawing substituents in the para position of the phenyl ring affect the NLO response indicating ICT as one of the controlling processes. (C) 2008 Elsevier B.V. All rights reserved.