For problems of matrix effect and correction method in EDXRF technique, three kinds of bogus binary system of Ni-Cu, Ni-Zn and Cu-Zn were chosen as research analyte. Firstly, Lachance-Trail algorithm was employed to get binary influence coefficient. Then, experimental measurement was taken to achieve qualitative analysis of binary influence effect, and good coherence was obtained after comparison. Meanwhile, exponential fitting and logarithm fitting correction equation were established to correct the effects in (bogus) binary sample. Three groups of Ni-Cu duality samples were used to test the fitting method. Compared to the actual results, the relative error of Ni and Cu was less than 4% except the one influenced by branch-ratio deduction method.