Solution cathode glow discharge-atomic emission spectrometry (SCGD-AES) was evaluated for its ability to determine toxic heavy metals, including cadmium (Cd), mercury (Hg), lead (Pb), and chromium (Cr), in environmental and biological samples. A significant enhancement in heavy metal signal was observed by addition of a small amount of cetyltrimethylammoniumchloride (CTAC, C16H33 (CH3)3NCl) to the samples. The net intensity of atomic emission lines of Cd, Hg, Pb, and Cr increased by 2.1-, 4.8-, 6.6-, and 2.6-fold, respectively, after addition of 0.15% CTAC to the test solutions. The effects of ionic surfactants (CTAC) compared with non-ionic surfactants, e.g., Triton x-45 and Triton x-100, on the sensitivity of Cd, Hg, Pb, and Cr were also investigated in the present study. The enhancement effect is in the order Triton x-45<Triton x-100<CTAC for Hg, Pb and Cr and Triton x-45<CTAC<Triton x-100 for Cd. Addition of CTAC to the electrolyte solutions decreased the background intensity and fluctuation of atomic emission lines of studied metals. It also changed the surface tension and the viscosity, and increased average discharge current of electrolyte solution. SCGD sensitivity to the heavy metals greatly improved by addition of the surfactant. The improved detection limits of Cd, Hg, Pb, and Cr were 1.0, 7.0, 2.0, and 42 ng mL(-1), respectively. The proposed method was validated by quantifying Cd, Hg, Pb, and Cr in certified reference materials, including human hair (GBW 09101b) and stream sediment (GBW 07310 and GBW07311). Measurement results obtained for the determination of Cd, Hg, Pb, and Cr in the reference materials agreed well with reference values. This study improves the application of SCGD-AES in quantifying very low levels of Cd, Hg, Pb, and Cr from biological and environmental materials.