In this paper, the spherical Fe-C micro-electrolysis materials (Fe-C MEM) were prepared using iron powder, activated carbon powder, corn straw, and bentonite as the raw materials. The preparation conditions optimized by single factor test showed Fe-C MEM had a high crystal violet removal and strength under 1:1 of Fe/C ratio, 2% corn straw content, 25% bentonite content, and 900 °C sintering temperature. The porous Fe-C MEM had a high specific surface area of 108.069 m2/g with an even distribution of zero-valent iron and carbon. The maximum removal capacity of CV by Fe-C MEM was 105.48 mg/g at 25 °C. The CV removal was a spontaneous endothermic process. The mechanism of CV removal by Fe-C MEM was adsorption combined with degradation. Fe-C MEM has a good performance in dye wastewater treatment.