Control of the radiative properties of functional molecules near metals is a key issue in nano-optics, and is particularly important in the fields of energy transfer and light manipulation at the nanoscale and the development of plasmonic devices. Despite the various vibronic transitions (S1 (vvariant prime) arrow right S0 (v)) available for frequency tuning of fluorescence, the molecular emissions near metals reported to date have been subject to Kasha's rule, with radiative decay from the lowest excited state (S1 (0)) (refs 6-10). Here, we show resonant hot electroluminescence arising directly from higher vibronic levels of the singlet excited state (S1 (vvariant prime > 0)) for porphyrin molecules confined inside a nanocavity in a scanning tunnelling microscope, by spectrally tuning the frequency of plasmons. We also demonstrate the generation of unexpected upconversion electroluminescence. These observations suggest that the local nanocavity plasmons behave like a strong coherent optical source with tunable energy, and can be used to actively control the radiative channels of molecular emitters by means of intense resonance enhancement of both excitation and emission.