The invention discloses a surface assistant laser desorption ionization mass spectrometry analysis method for improving desorption ionization efficiency of analyte by enriching the analyte to a metal nanocone array tip, and belongs to the technical field of detection. A metal membrane is applied to the surface of a silicon nanocone array in an evaporation manner, then surface plasma element conduction is carried out, photon energy is accumulated in tip positions, and thus a photon library is formed. As the surface is modified with fluoro-substitution alkyl sulfhydryl, a substrate has a large contact angle and a small rolling angle, then the friction of water droplets on the substrate is very small, analyte molecules of a solution are preferentially concentrated at the tips, and the utilization rate of laser energy can be further increased. Therefore, when the silicon nanocone array covered by the metal membrane modified with the fluoro-substitution alkyl sulfhydryl is used as substrate detection analyte molecules, the laser energy can be sufficiently absorbed and effectively utilized, furthermore the desorption ionization efficiency of the analyte molecules can be improved, and the method is applicable to various types of molecules.