Mixotrophic denitrification coupled biological denitrification with iron and carbon micro-electrolysis (IC-ME) is a promising emerging bioprocess for nitrate removal of biologically enhanced treated coal gasification wastewater (BECGW) with low COD to nitrate ratio. TN removal efficiency in R1 with IC-ME assisted was 16.64% higher than R2 with scrap zero valent iron addition, 23.05% higher than R3 with active carbon assisted, 30.51% higher than R4 with only active sludge addition, 80.85% higher than R5 utilizing single IC-ME as control. Fe2+ generated from IC-ME decreased the production of N2O and enriched more Nitrate-reducing Fe(II) oxidation bacteria (NRFOB) Acidovorax and Thiobacillus, which could convert nitrate to nitrogen gas. And the presence of Fe3+, as the Fe2+ oxidation product, could stimulate the growth of Fe(III)-reducing strain (FRB) that indicated by redundancy analysis. Microbial network analysis demonstrated FRB Geothrix had a co-occurrence relationship with other bacteria, revealing its dominant involvement in nitrate removal of BECGW.