We present energy spectra of electrons formed in the reaction of He(23S, 21S) with NO2which have significantly improved counting statistics and resolution compared to earlier work. Further, we show spectra of the fluorescence light emitted in these reactions. The data are recorded in the same molecular beam apparatus as the electron spectra. For the metastable singlet state He(21S) the spectra have not been measured before. We find that in addition to ionization excitation transfer takes place into Rydberg states of NO2**. Subsequently, the highly excited NO2** molecules dissociate into NO and atomic O* Rydberg atoms.