Abstract: Four reference materials were synthesized using highpurity materials. The certified values for 29 elements, including Ti, V, Mn, Cr, Co, Ni, Cu, Zn, As, Pb, Bi, Rb, Sr, Y, Zr, Nb, Mo, W, Nd, Ta, Hf, Yb, Sn, Ba, Cs, Ga, Ge, La, Ce were provided in the four reference materials. The content range for different elements in these reference materials was 0.00x%～8%. The use of the four reference materials could modify and adjust the interference coefficients, which settled the troubles of interference calculation among elements and emendation of the instrument. Compared to the use of single element reference materials, less number of reference materials could be used and higher analysis efficiency could be obtained. The homogeneity and stability were tested for the reference materials and the results showed that these reference materials were homogeneous and stable. These reference materials have been approved as the national reference materials by General Administration of Quality Supervision & Inspection and Quarantine of China.