AbstractThe hydrogen evolution reaction (HER) is a fundamental process that impacts several important clean energy technologies. Great efforts have been taken to identify alternative materials that could replace Pt for this reaction or that may present additional functional properties such as optical activity and advanced electronic properties. Herein, a comparative study of the HER activity for ultrathin films of MoTe₂, MoSe₂, and their solid solutions on highly oriented pyrolytic graphite is reported. Combining advanced characterization techniques and density functional theory calculations with electrochemical measurements, it is shown that the chemical activity of the scarcely reactive 2H phases can be boosted by the presence of metallic twin boundaries. These defects, which are thermodynamically stable and naturally present in Mo‐enriched MoTe₂ and MoSe₂, endow the basal plane of the 2H phase with a high chemical activity, which is comparable to the metastable 1T polymorph.