Many fundamental processes of structural changes at surfaces occur on a pico- or femtosecond timescale. In order to study such ultrafast processes, we have combined modern surface science techniques with fs-laser pulses in a pump–probe scheme. Grazing incidence of the electrons ensures surface sensitivity in ultrafast reflection high-energy electron diffraction (URHEED). Utilizing the Debye–Waller effect, we studied the nanoscale heat transport from an ultrathin film through a hetero-interface or the damping of vibrational excitations in monolayer adsorbate systems on the lower ps-timescale. By means of spot profile analysis, the different cooling rates of epitaxial Ge nanostructures of different size and strain state were determined. The excitation and relaxation dynamics of a driven phase transition far away from thermal equilibrium is demonstrated using the In-induced (8 × 2) reconstruction on Si(111). This Peierls-distorted surface charge density wave system exhibits a discontinuous phase transition of first order at 130 K from a (8 × 2) insulating ground state to (4 × 1) metallic excited state. Upon excitation by a fs-laser pulse, this structural phase transition is non-thermally driven in only 700 fs into the excited state. A small barrier of 40 meV hinders the immediate recovery of the ground state, and the system is found in a metastable supercooled state for up to few nanoseconds.