Abstract. Alkali-metal layers on semiconductor surfaces are model systems for metal-semiconductor contacts, Schottky barriers, and metallization processes. The strong decrease of the work function as a function of alkali-metal coverage is also technically made use of. Recently, however, interest in these systems is growing owing to ongoing controversial discussions about questions like: Is the adsorbate system at monolayer coverage metallic or semiconducting, and does the metallization take place in the alkali overlayer or in the top layer of the semiconductor? Is the bonding ionic or covalent? What ist the absolute coverage at saturation? What are the adsorption sites? Do all alkali metals behave similar on the same semiconductor surface? We try to answer some of the questions for Li, Na, K and Cs on Si(lll)(2 x 1), K and Cs on Si(lll)(7 × 7) and on GaAs(ll0), and Na and K on Si(100)(2 × 1) employing the techniques of direct and inverse photoemission. PACS" 71.30.+h, 73.40.Ns, 79.60.Gs The electronic structure of alkali metals on semiconductor surfaces is determined by the bonding properties within the interface. However, the bonding character, i.e. ionic or covalent bonding, is currently subject of a controversy, in particular for alkali metals on silicon surfaces. This concerns the amount of charge transfer from the alkali atom to the semiconductor, and also the question where a possible metallization takes place, i.e. in the alkali overlayer or within the top layer of the substrate. The increasing competition between the alkali-semiconductor and alkalialkali interaction as a function of coverage, both being dependent on the atomic radii and the polarizabilities of the * Present address: Bundesministerium ffir Forschung nnd Technologie, Heinemannstrasse 2, W-5300 Bonn 2, Fed. Rep. Germany ** Present address: Dept. of Synchrotron Radiation Physics, University of Lund, S-22362 Lund, Sweden *** Present address: Dept. of Natural Science, University of Karlstad, Box 9501, S-65009 Karlstad, Sweden alkali atoms, may determine the electronic properties of the interface.In general metal/semiconductor interfaces provide many technological applications ranging from photon detection over diode and/or rectifying functions to very-large-scale integrated circuits (VLSI). Relevant in this respect are silicon surfaces covered with simple metals (e.g. A1), transitions metals (V, Pd, Pt, etc.), and noble metals (Cu, Ag, Au) [1]. Despite their technical importance and known biasing properties these metal-semiconductor junctions provide a rather complex physical behavior on a microscopic scale. This is largely due to the temperature-dependent intermixing and silicide formation within the interfaces [2], particularly when transition-metals are deposited on silicon.Transition-metal silicides, however, are relatively easy to handle in ultra-high vacuum, as they stay clean and stable once prepared. Hence many of the research efforts have been devoted to these systems despite the fact that their interface chemistry, physics and morp...