The epitaxial growth of Ag on TiS₂(001) is characterized using reflection high-energy electron diffraction (RHEED), low-energy electron diffraction (LEED) and Auger electron spectroscopy (AES). Ag grows in the (111) orientation epitaxially on TiS₂(001) with Ag(110)//TiS₂(100). The growth mode belongs to the Volmer-Weber type, which means that Ag forms three-dimensional clusters on top of TiS₂(001). Ag also diffuses slowly into the substrate. The evolution of the electronic structure during this intercalation process is studied in detail with angle-resolved ultraviolet photoelectron spectroscopy (ARUPS) and X-ray photoelectron spectroscopy (XPS). The authors observed a striking difference between surface Ag and subsurface or intercalated Ag. They conclude that Ag atoms on TiS₂(001) have little interaction with the substrate, while upon intercalation charge transfer takes place from Ag to TiS₂. For comparison, they also studied Na and K at the TiS₂(001) surface. At low temperature (-140 degrees C), Na deposition results in an ordered ( square root 3* square root 3)R30 degrees superstructure. Na and K intercalation proceeds very rapidly. The Ti2p core-level spectra provide additional evidence that charge transfer has taken place after deposition and intercalation of Ag, Na and K.