The transition-metal dichalcogenide HfS₂ is a promising alternative semiconductor with adequate band gap and high carrier mobility. However, a controllable growth of continuous HfS₂ films with selectivity for specific surfaces at a low temperature on a large scale has not been demonstrated yet. Herein, HfS₂ films are grown at 100 °C by atomic layer deposition (ALD) based on the precursors tetrakis(dimethylamido)hafnium and H₂S. In situ vibrational spectroscopy allows for the definition of the temperature range over which (Me₂N)₄Hf chemisorbs as one monolayer. In that range, sequential exposures of the solid surface with (Me₂N)₄Hf and H₂S result in self-limiting reactions that yield alternating surface termination with dimethylamide and thiol. Repeating the cycle grows smooth, continuous, stoichiometric films of thicknesses adjustable from angstroms to >100 nm, as demonstrated by spectroscopic ellipsometry, XRR, AFM, UV–vis and Raman spectroscopy, XPS, and TEM. The well-defined surface chemistry enables one to deposit HfS₂ selectively using, for example, patterns generated in molecular self-assembled monolayers. This novel ALD reaction combines several attractive features necessary for integrating HfS₂ into devices.