Copper arsenate, substantially free from impurities that form sludge in wood preservatives such as chromated copper arsenate, is prepared by adding a solution of soluble arsenate to copper sulfate solution, either or both solutions containing sludge-forming impurities, to form a copper and arsenic-containing solution without precipitating copper arsenate. The pH during the adding is controlled at a value in the range of 1.8 to 2.2 to precipitate impurities. Precipitated impurities are removed, and the copper and arsenic-containing solution is neutralized with a suitable alkaline substance to pH 3.5 to 5.0 to precipitate copper arsenate. Arsenate solution is derived from arsenic oxides, soluble arsenic salts and compounds and metallurgical materials capable of yielding water-soluble arsenate. Copper sulfate solution is derived from crystals and compounds and metallurgical materials cable of yielding copper sulfate. In a preferred embodiment, sodium arsenate is derived by aqueous caustic oxidative pressure leaching of flue dusts and copper sulfate is derived by aqueous acid oxidative pressure leaching of copper matte.