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The article reports on a study of direct injection mass spectrometric confirmation of different drugs in overdose cases from postmortem blood through electrospray ionization-tandem mass spectrometry. It examined five cases of multiple-drug overdose which was measured by the West Virginia Office of the Chief Medical Examiner. It determined and measured 26 drugs and metabolites from the blood samples. It analyzed blood samples by diluting them to 0.1% formic acid or ammonium hydroxide in methanol before performing the electrospray ionization ion trap mass spectrometer. It also demonstrated the presence of different drugs and metabolites after the detection of internal standards.