Novel die-stacking schema using through-wafer vias may require thick electrodeposited copper and aggressive first-step chemical mechanical planarization (CMP). However, the effect of microstructural parameters, including surface orientation and grain size, on the CMP behavior of thick electrodeposited copper is not well understood. Here we explore the relationship between the surface orientation of copper grains and local CMP removal parameters using electron backscatter diffraction and topography correlation techniques. In the present work, solid copper disks are studied which are annealed to produce samples with differing grain sizes. In addition, aggressive CMP is performed on copper films (30 μm) electrodeposited on silicon. At the bulk level, the slurry composition is found to have the greatest effect on the removal rate and surface roughness. At the microstructural level, the nature of the grain boundaries (e.g. coincidence site lattice (CSL) vs. non-CSL boundaries) is shown to impact the depth of grooving at the grain boundaries. A relationship between surface orientation and local removal rate is found.