The invention relates to the field of biological removal of nitrogen, and aims to provide a enrichment method of microbes used for biologically removing high-concentration nitrogen-containing compounds. The method comprises the steps that a variety of practical anaerobic sludge from wastewater treatment plants is mixed, stirred, filtered and centrifuged, and then an inoculating source is obtained; chemical reagents are added into the inoculating source for inoculation in a microbial fuel cell, and then the microbial fuel cell runs; finally, the microbes used for biologically removing high-concentration nitrogen-containing compounds are enriched in the fuel cell. According to the enrichment method, the microbial fuel cell serves as a carrier, the nitrating and denitrifying microbes can stably grow and largely proliferated in a specific culture environment in a bioelectrochemistry mode, and are be absorbed on a cell electrode to form a dense membrane structure, and then the effect that the high-concentration nitrogen-containing compounds can be efficiently removed is achieved. In the method, a variety of practical wastewater is introduced, the microbial population is enriched, and the stability of the system is improved; the environment beneficial to the growth and propagation of the nitrating and denitrifying microbes is built, a selective effect is achieved on the microbial population, and the enrichment aim is achieved.