In recent years, many articles describing the preparation of supported colloidal catalysts have been published. The semi‐hydrogenation of alkynes to yield cis‐alkenes is often used as a test reaction in these publications. Many highly selective catalysts are described. However, a satisfactory explanation for the high reported selectivity has never been shown. Here we report a study on the possible effects that lead to the large selectivity differences between current commercial Pd/C catalysts and our newly developed NanoSelect catalysts. The focus is on differences in chemical composition as well as catalyst characteristics. We use a focused ion beam scanning electron microscope (FIB‐SEM) to locate the metal particle with respect to the surface of the support. FIB‐SEM analysis clearly shows the absence of the active component inside the support material, which could explain the high observed selectivity. Nevertheless, an effect of the stabilizer cannot be ruled out.