We demonstrate the observation of neutral dissociation, which provides the possibility of a spectroscopy of highly lying superexcited states. The yield spectrum of the undispersed fluorescence radiation of wavelength lambda(f) in the region 113 less than or equal to lambda(f) less than or equal to 180 nm from excited neutral fragments in the photodissociation of N2O is presented in the region of excitation photon wavelength lambda(ex) in the region 30 less than or equal to lambda(ex)less than or equal to 111 nm (photon energy region 41.3-11.2 eV). We show the evidence of selective or preferential neutral dissociation in the decay of superexcited N2O in competition with autoionization; in particular, the evidence for an important role of neutral dissociation of superexcited N2O followed by the production of ionic fragments. We also show the neutral dissociation of superexcited states with the character of double-holed doubly excited states located for 30 less than or equal to lambda(ex)less than or equal to 60 nm. The aspect of superexcitation (bound channel of electron promotion) in the region of inner-valence excitation is discussed in relation with free (continuum) channels.