The removal of COD in traditional Chinese medicine extraction wastewater was experimentally investigated at the scene using electro-biological technology. The COD removal rates under different hydraulic retention time (HRT) and different voltage were studied. Under the optimum operating conditions, the microbial diversity and structure of the biofilm near the anode and cathode plates were investigated by high-throughput 16S rRNA sequencing. The results indicated that under the dynamic conditions of HRT for 12, 24 and 36 h, the removal rates of COD in traditional Chinese medicine extraction wastewater were 70.78%±2.41%, 82.83%±1.76% and 92.62%±1.28% , respectively. Under the static conditions that the voltage was 0, 10 and 27 V, the COD removal rates of wastewater were 56.85%, 98.97% and 33.33% after 24 h processing, respectively. Bacterial species detected in these samples covered 29 phyla，54 classes，119 orders，219 families，413 genera. Taxonomic assignment analysis indicated that Proteobacteria, Bacteroidetes, Firmicutes, Chloroflexi, Epsilonbacteraeota near the anode and cathode plates at phylum level accounted for 94.6% and 99.4%, respectively. There were significant differences between the anode and cathode plates in microbial community structure at genus lever. Desulfobulbus, Lentimicrobiaceae, Sphaerotilus, Geobacter, Methyloversatilis, etc had relatively high relative abundances near the cathode plate, while its relative abundances in the anode plate were less than 1%. Zoogloea, Acinetobacter, Fusibacter, etc were relatively abundant near the anode plate. Analysis showed that the electro-biological coupling technology could effectively degrade traditional Chinese medicine extraction wastewater compared with only under the treatment process of microorganisms or electrochemistry. Zoogloea was the main different microorganism near the anode and cathode plates.