► Enhanced magnetization (MS=1.6emu/g) in Co-doped BiFeO3is observed. ► XAFS results show that partial Fe ions occupy Bi-sites of BiFeO3and Co ions occupy Fe-sites. ► The ratio (fitted by XAFS) of Fe ions at Bi site to the whole Fe ions is about 9.4%. ► The existence of divalent Fe2+ions and the structural distortion are demonstrated. ► Partial Fe ions at Bi site and lattice distortion are the possible main reasons of enhancedMS.