Catalytic selectivity in the epoxidation of ethylene to form ethylene oxide on alumina-supported silver catalysts is dependent on the geometric structure of catalytically active Ag particles and reaction conditions. Shape and size controlled synthesis of Ag nanoparticles is used to show that silver nanocubes exhibit higher selectivity than nanowires and nanospheres. For a given shape, larger particles offer improved selectivity. The enhanced selectivity toward ethylene oxide is attributed to the nature of the exposed Ag surface facets; Ag nanocubes and nanowires are dominated by (100) surface facet and Ag nanospheres are dominated by (111). Furthermore, the concentration of under-coordinated surface sites is related to diminished selectivity to ethylene oxide., We demonstrate, that a simple model can account for the impact of chemical and physical factors, on, the reaction selectivity. These observations have also been used, to design a selective catalyst for the ethylene epoxidation reaction.