The paper presents the original technique of trace analysis of solid cadmium samples by the optical emission spectrometry with inductively coupled plasma in combination with the electrothermal vaporization (ETV-ICP-OES). The temperature program for heating ETV provides almost complete evaporation of cadmium (at 900 °C) and the subsequent vaporization of analytes when the temperature ETV rises up to 2400 °C. Separate vaporization of matrix and analytes provides reducing of spectral interferences, which ensures lower the limits of detection of the analytes (LODs). Evaluation of the analytical characteristics of the proposed technique shows that the ETV-ICP-OES allows us to reduce the detection limits of Al, Au, Be, Bi, Co, Cr, Fe, Ga, In, Mn, Ni, Re, Sn and V from 3 to 670 times compared with traditional ICP-OES analysis of 2% cadmium solutions. The accuracy of proposed technique was confirmed by analysis of cadmium samples by an independent ICP-MS technique and by addition and recovery experiment.