The application of femtosecond laser photoemission to the study of electron dynamics at semiconductor surfaces and interfaces is described. Fundamental processes such as electron-electron and electron-phonon scattering, diffusion and recombination are discussed. The dynamical evolution of photoexcited electrons on the As/Ge(111) surface is studied with broadly tunable harmonics. Extension of high harmonic generation to produce photon energies approaching 80 eV have resulted in the first atomic core level photoemission spectra from a tunable femtosecond source. Possible applications of harmonics to studies of surface photochemistry are discussed.