In this study, Fe/C internal electrolysis was used to pretreat the wastewater of lead 2, 4, 6-trinitroresorcinate (LTNR) production. The influences of pH, acids, reaction time and Fe/C volume ratio on COD removal were investigated. The optimum condition of iron-carbon electrolysis was determined by orthogonal experiment. And the reaction kinetics of COD removal and mechanism of contaminant removal were preliminary explored. The results showed that wastewater pH adjusted by sulfuric acid was more economical and better for COD removal. The effect of pH is the greatest. Two processes programs (pH3, Fe/C volume ratio 1.0, reaction time 24hr; pH3, Fe/C volume ratio 1.2, reaction time 18hr) are advised in project. Under the two process conditions, COD removal rates are 73.78% and 72.42%, respectively. The COD removal could be well described by pseudo-second-order kinetic model, and the reaction rate constant is 2.804×10-4 L/(mg·hr). Within the range of 0-24hr, film diffusion is the rate controlling step of the electrolysis process. The degradation process of trinitroresorcinate may be as follow: trinitroresorcinate→nitroaniline phenol or phenol aniline →nitrobenzene quinone or benzoquinone and ammonia→biodegradable or inorganics and nitrate.