A method to perform photoelectron spectroscopy (PES) on systems at high temperatures and with a high saturation vapor pressure is presented. The basic concept consists of a time-resolved data acquisition following pulsed laser heating and melting of the sample surface. With this technique it is possible to get access to samples under conditions which normally would not be compatible with the requirements of PES. A standard electron spectroscopy for chemical analysis spectrometer has been equipped with additional electronics to allow time-resolved measurements. A small spot monochromated x-ray photoelectron spectroscopy source is used for the core-level spectroscopy and a modified gas discharge lamp for excitation of the valence band. The first results of valence-band spectra taken with this method are shown for germanium and silicon and its feasibility even in core-level spectroscopy is shown in the case of germanium.