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The valence band structure of the layered transition metal dichalcogenide WS₂ has been determined experimentally by angle resolved photoelectron spectroscopy and theoretically by augmented spherical wave band structure calculations as based on density functional theory. Good agreement between experimental and calculated band structure is observed for single crystal WS₂. An experimental band structure of a single layer was determined from an electronically decoupled film prepared on a single crystalline graphite substrate by metal-organic van der Waals epitaxy. The polarization dependent photoemission selection rules of the single layer film are appropriate for a free standing film. The experimental single layer band structure shows some differences compared to band structure calculations using bulk atomic positions within the layer. We conclude that relaxation of the single layer occurs as a consequence of the missing interlayer interactions leading to close agreement between electronic structure of the single layer and single crystal. As a consequence of the missing interlayer interactions the valence band maximum for the single layer is located at the K point of the Brillouin zone.