High-field conditioning is the process by which radio-frequency structures in particle accelerators and other high-gradient devices reach their operating fields, yet the underlying physical mechanism remains an open question. Models and indirect measurements point to subsurface dislocation dynamics, but large-area structural measurements have been missing. We present electron backscatter diffraction measurements spanning millimeter-scale regions on a copper cathode conditioned at pulsed direct-current fields up to ~80 MV/m in a sloped-anode geometry, which imposes a known gradient of field exposure across a single electrode. Across nine regions of interest spanning this exposure range, the mean intragrain misorientation of field-exposed regions exceeds that of unexposed references by ~75%; the difference is reproduced by three independent misorientation metrics and confirmed by Kolmogorov-Smirnov tests. To our knowledge, this is the first large-area observation of structural differences between conditioned and unconditioned regions of a high-field electrode. The misorientation separates into three tiers (high-field center and edge, low-field periphery, and unexposed reference) that match the spatial profile of the conditioning-state variable $E_S$ predicted by Monte Carlo simulations. These observations point to the evolving subsurface dislocation population as a candidate physical basis of conditioning.