We present a single-step ligand-directed colloidal synthesis protocol for the selective growth of dimensionally- and shape-controlled niobium disulfide (NbS2) nanostructures. A systematic modulation of the reaction conditions resulted in the development of monolayer nanosheets, which alternatively grew as laterally confined (<100 nm) 2D nanostructures using an appropriate mixture of coordinating ligands with different functional groups. The lateral size reduced to ∼50 nm by increasing the amount of a chalcogen source (carbon disulfide, CS2), which promoted planar growth to form 0D nanohexagons and 1D hexagonal nanorods. A noncoordinating solvent suppressed anisotropic growth and resulted in the formation of 0D nanospheres. Nanohexagons with the highest fraction of corner and edge active sites delivered the highest activity in dibenzothiophene hydrodesulfurization. © 2018 American Chemical Society, reprinted with permission.