The invention relates to an electro-polymerizable chemically-modified electrode organic material and application of the electrode organic material in ultra-trace TNT (Trinitrotoluene) detection and belongs to the field of electrochemical sensing technologies. The structural formula of the organic material is shown in the specification, wherein the molecular main chain skeleton consists of an A and two side units B. The A can be pyrene, naphthalene, anthracene, an anthracene derivative, phenanthrene, dibenzo-quinoxaline or the like; each B can be benzene, biphenyl, phenylene vinylene, fluorene or the like; each unit C is an electro-active unit and can be furan, pyrrole, thiophene, carbazole, diphenylamine, triphenylamine or the like. A connecting chain R for the molecular main chain skeleton and electrochemically-polymerized groups can be an alkyl chain, alkoxy chain or oxy chain. Carbazolyl groups can be subjected to crosslinking during electrochemical polymerization, and molecules can form spherical micro-nano structures due to crosslinking, so that on one hand, the contact specific surface area between the molecules of the organic material and TNT molecules is increased, on the other hand, due to pore structures formed among the micro-nano structures, TNT molecule diffusion paths are increased, and electrical signal response is enhanced.