In this study, the slow speed shear test in both Sn-3.0Ag-0.5Cu (wt%)/OSP Cu and Sn-3.0Ag-0.5Cu-0.1Ni (wt%)/OSP Cu assembly with the ball heights of 300 μm and the corresponding grain structures were investigated. With the aid of Electron Back Scattering Diffraction (EBSD) analysis, single grain structure was observed in Sn-3.0Ag-0.5Cu/OSP Cu. Besides, Ni was found to control the grain structure in Sn-3.0Ag-0.5Cu-0.1Ni solder balls, showing multiple grains with partially interlaced structure. The grain variation resulted from larger undercooling caused by smaller ball size and Ni-dopant induced tiny intermetallic compounds (IMCs). IMCs serve as heterogeneous nucleation sites for β-tin and thus alter the grain structure of solder balls. The results of shear test reveal that the peak force of solder joints was efficiently enhanced by the addition of Ni. The enhancement of mechanical strength was attributed to the modification of grain structure by the introduction of Ni dopant. It is believed that the smaller grains, tiny intermetallic compounds, and the oriented interlaced area in Ni-doped solder joints became energy barriers for propagation of cracks and dislocations. It is demonstrated that Ni-doped solder joints tend to exhibit better mechanical reliability in advanced electronic packaging.