In this paper we advance a theory of inverse electronic relaxation (IER) induced by high-order multiphoton excitation of collision-free molecules. The IER process involves spontaneous one-photon radiative decay of molecular eigenstates. These states originate from intramolecular scrambling of vibronic levels corresponding to the ground state electronic manifold with a discrete vibronic level (or a set of such levels) which belong to a low-lying excited electronic state. For a diatomic molecule and for a small polyatomic the molecular eigenstates are excited by a coherent multiphoton excitation process, while for larger polyatomic molecules where the low electronically excited state corresponds to an intermediate level structure or to the statistical limit, incoherent multiphoton excitation of the molecular eigenstates of an "isolated" molecule prevails. Explicit expressions for the rate of IER are derived and the conditions for the observation of this novel phenomenon are established.