Grain boundary structures in the Accumulative roll-bonding (ARB) processed copper (ARB-Cu) have been studied. The grain boundary structures were observed by high-resolution transmission electron microscopy (HRTEM). In order to clarify the difference between the grain boundaries in ARB-Cu and equilibrium boundaries, calculated atomic structure of symmetric tilt grain boundaries with <110> common axis <110> symmetric tilt grain boundary; <110> STGB) in Cu were used. The near 14° boundary in the ARB-Cu could be described by the dislocation model, but the dense dislocation region existed near the grain boundary. The high angle boundaries in ARB-Cu could be described by the structural units which were obtained by molecular dynamics (MD) simulation. Furthermore, in the 2 cycles and 6 cycles ARB-Cu (2cARB-Cu and 6cARB-Cu), the deformation twin boundaries could be observed and described by the structural unit. Therefore, it was concluded that the grain boundary structure in the ARB-Cu was not much different from the normal equilibrium grain boundary and explained by conventional dislocation and structural unit models.