Grain boundary character distributions (GBCD) of OFHC copper equal-channel angular pressing (ECAP) deformed and then annealed were analyzed by electron back scatter diffraction (EBSD). The experimental results showed that a combination of ECAP deformation and annealing treatments could significantly increase the fraction of low-Σ coincidence site lattice (CSL) boundaries (Σ≤29) and effectively interrupt the connectivity of random boundaries network in OFHC copper. An increase of low-Σ CSL boundaries from 45.27 to 71.06% was observed in as-received material after one pass ECAP strain followed by annealing at 350 °C for 48 h. The connectivity of random boundaries network was interrupted by high fraction of low-Σ CSL boundaries.