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The electronic band structure of extremely thin (from 1 to 8 monoatomic layer (ML) thick) epitaxial Pb(111) films grown at low temperatures in ultrahigh vacuum (UHV) condition on Si(111)-(6×6)Au substrate is studied with angle-resolved photoelectron spectroscopy (ARPES). The morphology of the Pb film is determined with scanning tunneling microscopy (STM). Normal-emission photoelectron spectra recorded at the sample temperature of 130 K reveal quantum well states (QWS) characteristic of quantization perpendicular to the film surface. The energies of these states as a function of the number of the Pb(111) monoatomic layers are determined and compared with calculated in terms of the Bohr–Sommerfeld phase accumulation model.