AbstractRecent progress in the synthesis of monolayer MoS₂, a two-dimensional direct band-gap semiconductor, is paving new pathways toward atomically thin electronics. Despite the large amount of literature, fundamental gaps remain in understanding electronic properties at the nanoscale. Here, we report a study of highly crystalline islands of MoS₂ grown via a refined chemical vapor deposition synthesis technique. Using high resolution scanning tunneling microscopy and spectroscopy (STM/STS), photoemission electron microscopy/spectroscopy (PEEM) and μ-ARPES we investigate the electronic properties of MoS₂ as a function of the number of layers at the nanoscale and show in-depth how the band gap is affected by a shift of the valence band edge as a function of the layer number. Green’s function based electronic structure calculations were carried out in order to shed light on the mechanism underlying the observed bandgap reduction with increasing thickness, and the role of the interfacial Sulphur atoms is clarified. Our study, which gives new insight into the variation of electronic properties of MoS₂ films with thickness bears directly on junction properties of MoS₂, and thus impacts electronics application of MoS₂.