The microstructures of cryogenically ball-milled Cu were investigated by high-resolution electron microscopy. It was found that the grain-size reduction is a dislocation-controlled continuous process which consists of the formation of small-angle grain boundaries (GBs), a gradual increase in misorientations as a result of accumulation of more dislocations and, finally, the formation of large-angle GBs. The GBs were generally curved, wavy or faceted, and heavily strained, which are typical characteristics of nanostructured materials. In addition, extrinsic dislocations were found in many GBs, indicating that most are in a high-energy non-equilibrium configuration, which is consistent with observations in equal-channel angular pressing processed Cu, Ni, and Al-Mg, repetitive corrugation and straightening processed Cu and room-temperature ball-milled Cu. These results support a still-disputed concept that GBs in nanostructured metals processed by severe plastic deformation are mostly in non-equilibrium states.