A 4H structural silver nanowire (4H-AgNW) is discovered to coexist with a face-centered cubic (FCC) one prepared by electrochemical deposition and to have the highest concentration in the total of 4H- and FCC-AgNWs with diameters around 30 nm. Moreover, the concentration becomes smaller when the diameters deviate from 30 nm. This size effect arises from the fact that 4H-AgNW has a more favorable surface configuration but higher volume internal energy than FCC-AgNW, which is proved by our model.