Characterizing the residual stress of thick nanocrystalline electrodeposits poses several unique challenges due to their fine grain structure, thickness distribution, and matte surface. We use a three-dimensional profilometry-based approach that addresses each of these complicating factors and enables quantitative analysis of residual stress with reasonable accuracy. The specific emphasis of this work is on thick (10–100 μm), nanocrystalline Ni-W electrodeposits of the finest grain sizes (4–63 nm), in which residual stresses arise during the deposition process as well as during postdeposition annealing. The present measurements offer quantitative insight into the mechanisms of stress development and evolution in these alloys, suggesting that the grain boundary structure is out of equilibrium (unrelaxed) and contains the excess free volume that controls the resulting residual stress levels in these films. There are apparently two factors contributing to this stress: the percentage of excess free volume contained in the grain boundaries, which is affected by the processing conditions, and the total volume fraction of grain boundaries, which is controlled by the grain size.