By means of annealing at different temperatures, the copper wires with various numbers of grain boundaries were achieved. And the resistivity of copper wires was measured. The results show that with increasing the number of grain boundaries, the resistivity of copper wires increases, the relationship between the number of grain boundaries and the resistivity of cooper wires can be expressed as y=1.86×10-8e-0.90/x. Unlike dislocation and lattice vacant sites, the curve of the grain boundary vs the resistivity is not linear. Grain boundary controls the general trend of the curve, but the type and the quantity of impurity controls the details of the curve.