The invention discloses a mass spectrometric nano-spray electrode, a manufacturing method and the application thereof. The mass spectrometric nano-spray electrode is composed of a fused quartz capillary tube and a CNT (carbon nanotube) doped sol-gel composite material, wherein the CNT doped sol-gel composite material is coated on an outlet end of the capillary tube. The method for manufacturing the electrode comprises the following steps: firstly, carrying out pretreatment on the used fused quartz capillary tube and the CNT; then, preparing sol doped with the CNT; and finally, coating the outlet end of the fused quartz capillary tube with the sol, and carrying out solvent volatilizing and aging. The mass spectrometric nano-spray electrode disclosed by the invention has the advantages of good stability, high sensitivity, long service life, high reusability, simpleness for manufacturing, low cost, and capability of continuously realizing nano-spray for 52 hours and continuously being used 170 hours, and the like and can be continuously used for 170 hours, and the mass spectrometric results have good reproducibility; and the mass spectrometric nano-spray electrode can be used in CE (capillary electrophoresis) or capillary LCMS (liquid chromatography-mass spectrometry) analysis technique, and also can be used in a nano-spray mass spectrographic analysis technique.