This report describes a series of reaction deposition studies directed toward the formation of oriented or epitaxial tungsten films on single‐crystal tungsten by the hydrogen reduction of tungsten hexafluoride at low pressure. In addition, a novel method for controlled etching of tungsten by tungsten hexafluoride for surface pretreatment and as a tool for elucidating metallurgical structure is given. The use of this hexafluoride etching technique for surface pretreatment does not insure oriented deposition, but with the proper control of other factors such as system cleanliness, reactant material purity, deposition rates, etc., oriented or epitaxial deposits have been formed.