Electroplated Cu was found to have a fine as-plated microstructure, 0.05 ± 0.03 μm, with multiple grains through the film thickness and evidence of twins and dislocations within grains. Over time at room temperature, the grains grew to greater than 1 μm in size. Studied as a function of annealing temperature, the recrystallized grains were shown to be 1.6 ± 1.0 μm in size, columnar and highly twinned. The grain growth was directly related to the time dependent decrease in sheet resistance. The initial grain structure was characterized using scanning transmission electron microscopy (STEM) from a cross-section sample prepared by a novel focused ion beam (FIB) and lift-out technique. The recrystallized grain structures were imaged using FIB secondary electron imaging. From these micrographs, the grain boundary structures were traced, and an image analysis program was used to measure the grain areas. A Gaussian fit of the log-normal distribution of grain areas was used to calculate the mean area and standard deviation. These values were converted to grain size diameters by assuming a circular grain geometry.