The invention discloses a method for removing and recovering arsenic from lead anode slime, which comprises the following steps of: performing screening, hot water washing and baking on the lead anode slime, performing oxidation leaching by controlling potential in sodium hydroxide solution, oxidizing the arsenic by using compressed air and hydrogen peroxide as oxidants respectively, adding the oxidized arsenic into alkaline leachate, and ensuring metals such as bismuth, lead, stibium and copper are oxidized and then enter alkaline leaching residue together with noble metals; and after alkaline oxidization leaching process is finished, filtering while hot, performing cooling crystallization on the leachate to generate sodium arsenate crystals, supplementing certain sodium hydroxide to crystallization mother liquor, returning the crystallization mother liquor to the leaching process, and separating and recovering the arsenic and other valuable metals from the lead anode slime. The arsenic leaching rate is over 98.0 percent and the secondary arsenic pollution is free; and the method has the advantages of low requirement on equipment materials, safe operation, low labor intensity, short treatment time and good operating environment.