The chemical forms of mercury (Hg), particularly methylmercury (MeHg), in songbird feathers from an abandoned mining region were analyzed via X-ray absorption near-edge structure analysis (XANES). In feathers, proportions of MeHg as total mercury (75.6–100%) quantified by the XANES were directly comparable to the chemical extraction values (74.1–95.9%). Most of MeHg were bound with cysteine (Cys) and reduced glutathione (GSH), whereas inorganic mercury (IHg) was mainly bound with GSH. These results were consistent with those found in fish muscles and human hairs of both fish consumers and occupational Hg exposure populations. Our study suggested that chemical forms and speciation of Hg were highly dependent on the exposure sources and food consumption, respectively. Bird feathers were able to selectively accumulate MeHg due to their special binding ways. However, detailed mechanisms of Hg accumulation in bird feathers remain to be further elucidated.