Matrix effect in the determination of trace metallics in high-purity copper has been evaluated for estimation of Ag, Cr, Fe, Ni, Ph, Sb and Zn by FAAS and GFAAS. Matrix effects were less significant for FAAS while it was quite important for GFAAS. Methods have been standardized for determination of various trace elements after separation of matrix element and pre-concentration of the analytes. For separation of matrix two different procedures were standardized: (i) co-precipitation of metal hydroxides using La as carrier and (ii) electro deposition. To validate the method, the recovery of metal ions were tested and were found to be satisfactory. The methods have been applied to the determination of these impurities in high-purity copper samples. For the determination of silver, a selective deposition method was adopted in order to avoid co-deposition of copper. These three different modes of matrix separation were found to be complementary to each other for determination of various critical trace elements in high-purity electrolytic copper.