Void formation in the Cu-Sn system has been identified as a major reliability issue with small volume electronic interconnects. Voids form during the interdiffusion of electrochemically deposited Cu and Sn, with varying magnitude and density. Electroplating parameters include the electrolytic chemistry composition and the electroplating current density, all of which appear to effect the voiding characteristics of the Cu-Sn system. In addition, interfacial voiding affects the growth kinetics of the Cu3Sn and Cu6Sn5 intermetallic compounds of the Cu-Sn system. The aim here is to present voiding data as a function of electroplating chemistry and current density over a duration (up to 72 h) of isothermal annealing at 423 K (150 °C). Voiding data includes the average interfacial void size and average void density. Voids sizes grew proportionally as a function of thermal annealing time, whereas the void density grew initially very quickly but tended to saturate at a fixed density. A morphological evolution analysis called the physicochemical approach is utilised to understand the processes that occur when a voided Cu/Cu3Sn interface causes changes to the IMC phase growth. The method is used to simulate the intermetallic thickness growths' response to interfacial voiding. The Cu/Cu3Sn interface acts as a Cu diffusion barrier disrupting the diffusion of Cu. This resulted in a reduction in the Cu3Sn thickness and an accelerated growth rate of Cu6Sn5.