Amorphous powders prepared by mechanical alloying were tested as heterogeneous catalysts in the 4-methylpentan-2-ol conversion into its dehydration and dehydrogenation products. The reaction was performed both in a conventional fixed-bed flow microreactor and in a modified milling vial used as a mechanochemical batch reactor. In the thermal catalytic tests several amorphous alloys, CuM (M = Ti, Zr, Hf), PdZr, and CuPdZr were employed as catalysts. Pretreatment conditions and catalytic runs induced different structural evolution in the tested systems. A correspondence was observed between structural modifications and catalytic properties. The mechanochemical trials were performed over a-Cu40Hf60 powders. Conversion and selectivity results were found to depend on the impact energy. The determination of the milling dynamics parameters allowed evaluation of the mechanochemical activity and comparison of, on an absolute basis, the results of the catalytic trials performed by the two techniques.