The X-Ray Spectrometer (XRS) on the MESSENGER spacecraft measures elemental abundances on the surface of Mercury by detecting fluorescent X-ray emissions induced on the planet's surface by the incident solar X-ray flux. The XRS began orbital observations on 23 March 2011 and has observed X-ray fluorescence (XRF) from the surface of the planet whenever a sunlit portion of Mercury has been within the XRS field of view. Solar flares are generally required to provide sufficient signal to detect elements that fluoresce at energies above ∼2 keV, but XRF up to the calcium line (3.69 keV) has been detected from Mercury's surface at times when the XRS field of view included only unlit portions of the planet. Many such events have been detected and are identified as electron-induced X-ray emission produced by the interaction of ∼1–10 keV electrons with Mercury's surface. Electrons in this energy range were detected by the XRS during the three Mercury flybys and have also been observed regularly in orbit about Mercury. Knowledge of the energy spectrum of the electrons precipitating at the planet's surface makes it possible to infer surface composition from the measured fluorescent spectra, providing additional measurement opportunities for the XRS. Abundance results for Mg, Al, and Si are in good agreement with those derived from solar-induced XRF data, providing independent validation of the analysis methodologies. Derived S and Ca abundances are somewhat higher than derived from the solar-induced fluorescence data, possibly reflecting incomplete knowledge of the energy spectra of electrons impacting the planet.