Spectra of photoelectrons and thermionic electrons emitted from silicon during pulsed laser irradiation at energy densities encompassing the thresholds for laser annealing and damage are reported. Annealing is accomplished with a 90-nsec pulse of 532-nm light, which may be accompanied by a 266-nm probe pulse. A cylindrical mirror analyzer is used for energy resolution of emitted electrons. Time-resolved reflectivity at 633 nm verifies attainment of the high-reflectivity annealing phase. Spectral widths and total yields imply a modest electron temperature (T < 3000 K) during annealing. The data suggest that the work function of the silicon (111) face may increase about 0.6 eV upon transition to the molten phase.