The invention discloses a method for calcium-free calcination production of sodium chromate and chromium-containing cast iron as a co-product. The method comprises the following steps of 1, first-stage calcination by mixing chromite and soda ash according to a certain ratio to obtain a first-stage mixed material, wherein a soda ash use amount is 35-60% of the theoretical alkali use amount, putting the first-stage mixed material into a rotary kiln, carrying out oxidizing calcination, and carrying out impregnation and filtration of the calcined clinker to obtain a first-stage sodium chromate alkali solution and filter residues, and 2, treating the filter residues, and carrying out second-stage calcination and third-stage calcination of the filter residues by the step 1 to obtain second-stage calcination filter residues, third-stage calcination filter residues, a second-stage calcination sodium chromate alkali solution and a third-stage calcination sodium chromate alkali solution, wherein the third-stage calcination filter residues can be used for co-production of chromium-containing cast iron. The method does not adopt any auxiliary materials in calcination, and effectively avoids ring forming of the rotary furnace. The calcination residues obtained by the method does not contain hexavalent chromium compounds and thus chromium residue harmlessness and recycling are realized. Through co-production of high-carbon chromium iron, a chromium comprehensive use ratio is improved by more than 95%. Through smelting, produced electroslag does not contain hexavalent chromium so that thorough detoxification of chromium residues is realized.