The invention provides a harmless treatment method for recycling valuable metal and arsenic resources from arsenic-containing smoke. All valuable elements are recycled and utilized through the procedures of carrying out oxygen pressure leaching via caustic alkali; carrying out selective reduction purification on leachate; during purification, carrying out hydrogen reduction and vacuum distillation on obtained crude tellurium so as to obtain high-purity tellurium; after purification, obtaining a pure sodium arsenite solution, and using the solution for the arsenic salt purification of a zinc sulfate solution so as to remove cobalt and nickel; carrying out fluidization washing on leaching residues; after washing, solidifying arsenic in the solution, and carrying out reduction smelting on the residues; and carrying out oxidization blowing and the like. The arsenic is removed from the smoke, stibium, lead, bismuth, stannum and the like are kept in the residues from which the arsenic is removed as much as possible, and the deep separation of the arsenic and the stibium is realized. The obtained pure sodium arsenite solution is used for the arsenic salt purification of the zinc sulfate solution used for wet-process zinc smelting so as to remove the cobalt and nickel raw materials, part of sodium arsenate with high impurity content is solidified, the arsenic is precipitated, the harmless recycling of the arsenic resource is realized, and the valuable elements, such as the tellurium, the stibium, the lead and the bismuth are recycled. The comprehensive utilizing rate of the resources is high, the application range of the raw materials is wide, and a pollution problem in the extracting process of a traditional technology is solved.