We have designed and synthesized two families of γ-pyrone CC analogs presenting different electron-donating (hydroxy, alkoxy, amine) and electron-attracting (oxo, malonitrile) groups and absorbing in the UV-Vis window. Molecular modeling has shown that the topology of the most relevant PES is highly affected by the choice of the later substituent and that the presence of a malonitrile group opens totally new relaxation pathways driven by the photoactivated rotation of CN groups, efficiently competing with the ethylenic double bond isomerization.