The daytime photoelectron energy spectrum has been measured at altitudes above 154 km by the photoelectron spectrometer experiment on the Atmosphere Explorer-E satellite. Much higher energy resolution spectra than previous AE-C results have been obtained. Below 200 km, well resolved peaks are observed in the spectrum corresponding to production of O+ and N+2 in various electronic states from photoionization of N2 and O by solar He II (304A) radiation. Vibration-rotation excitation of N2 by inelastic electron scattering is observed at 2.5 eV. The features due to nitrogen disappear from the spectrum at altitudes above 200 km.