In recent years, solution cathode glow discharge atomic emission spectroscopy (SCGD-AES), a booming technique for metal element determination in aqueous solution, has a large quantity of notable characteristics, such as working under atmospheric pressure, easy simple injection, little size, small volume, low operating costs, and simultaneous detection of multi-metal-elements. According to our previous researches, the concentration of metal elements was relative to not only one of its characteristic spectral lines, but also the other characteristic spectral lines of itself or the characteristic spectral lines of other elements. In order to improve the detection capability and accuracy of solution cathode glow discharge atomic emission spectroscopy, reduce the matrix effect in the complex solution and make full use of spectral information, the multivariate linear regression method was employed to make a quantitative analysis of spectral information. Two characteristic spectral lines of Pb Ⅰ 368.35 nm and Pb Ⅰ 405.78 nm were employed to establish the binary linear regression equation; compared with standard curve method, the degree of fitting R2 increased to 0.998 7 from 0.986 5, and the relative errors of two test solutions decreased to 14.20% and 1.51% from 34.00% and 29.00%, respectively. Quaternary linear regression equation using Na Ⅰ 589.38 nm, Zn Ⅰ 213.80 nm, Pb Ⅰ 405.78 nm and Hβ were also built to reduce the matrix effect in the complex solution; compared with standard curve method, the degree of fitting R2 increased to 0.995 6 from 0.955 8, and the relative errors of two test solutions decreased to 2.33% and 3.57% from 11.67% and 14.71%, respectively. The above results indicate that: compared with standard curve method, multivariate linear regression method has the ability to reduce the influence of matrix effect in the complex aqueous solution, take full advantage of spectral information, improve degree of fitting (R2)and reduce the errors, thus improve the accuracy of metal elements determination with solution cathode glow discharge atomic emission spectroscopy.