Growth by chemical vapor deposition (CVD) leads to multilayer WS2 of very high quality, based on high-resolution angle-resolved photoemission spectroscopy. The experimental valence band electronic structure is considered to be in good agreement with that obtained from density functional theory calculations. We find the spin-orbit splitting at the K̄ point to be 420 ± 20 meV with a hole effective mass of -0.35 ± 0.02 me for the upper spin-orbit component (the branch closer to the Fermi level) and -0.43 ± 0.07 me for the lower spin-orbit component. As predicted by theory, a thickness-dependent increase of bandwidth is observed at the top of the valence band, in the region of the Brillouin zone center. The top of the valence band of the CVD-prepared films exhibits a substantial binding energy, consistent with n-type behavior, and in agreement with transistor characteristics acquired using devices incorporating the same WS2 material.