The intermetallic compound (IMC) evolution in Cu pad/Sn-Ag-Cu solder interface and Sn-Ag-Cu solder/Ni pad interface was investigated using thermal shock experiments with 100-μm-pitch flip-chip assemblies. The experiments show that low standoff height of solder joints and high thermomechanical stress play a great role in the interfacial IMC microstructure evolution under thermal shock, and strong cross-reaction of pad metallurgies is evident in the intermetallic growth. Furthermore, by comparing the IMC growth during thermal aging and thermal shock, it was found that thermal shock accelerates IMC growth and that kinetic models based on thermal aging experiments underpredict IMC growth in thermal shock experiments. Therefore, new diffusion kinetic parameters were determined for the growth of (Cu,Ni)6Sn5 using thermal shock experiments, and the Cu diffusion coefficient through the IMC layer was calculated to be 0.2028 μm2/h under thermal shock. Finite-element models also show that the solder stresses are higher under thermal shock, which could explain why the IMC growth is faster and greater under thermal shock cycling as opposed to thermal aging.