Pd25Cu75@SiO2 core-shell and PdCu@SiO2@Cu core-shell-satellite architectures were fabricated by silica-coating of Pd25Cu75 colloids in a reverse microemulsion. Hydrolysis of tetraethylorthosilicate in the reverse microemulsion containing hydrazine and ammonia yielded a core-shell structure, while the use of ammonia only, instead of a mixture of hydrazine and ammonia, formed a core-shell-satellite structure. The ammonia-leached copper species migrated onto the developing silica shell and formed smaller Cu clusters. Air-calcination at 673 K followed by H2-reduction at 773 K of the as-synthesized samples removed the organic surfactants and generated the permeable porous silica shells. The core-shell catalyst consisted of a metal core (8.5 nm) and a silica shell (7.8 nm), while the core-shell-satellite catalyst was composed by a metal core (7.0 nm), a silica shell (8.0 nm), and satellite Cu clusters (1.4 nm) on the silica shell. When used to catalyze the selective hydrogenation of acetylene to ethylene, the core-shell-satellite catalyst showed substantially enhanced activity and stability because of the synergetic catalysis between the metal core and the surrounding Cu clusters.