Novel bioflocculants (BS-MBF) were prepared using the wastewater supernatant from anaerobic co-digestion of corn straw and molasses wastewater as a nutrient resource. Acetic acid and ethanol were the dominant fermentation products during the anaerobic digestion process and were estimated to be 50.5% and 30.0%, respectively, after 150 d of operation. Equal volumes of bioflocculant producing bacteria F2 (Rhizobium radiobacter) and F6 (Bacillus sphaericus) were mixed to form F+, which was inoculated to wastewater supernatant at different times. A maximum flocculation activity of 91.3% was achieved, and 2.32 g/L of purified bioflocculant was extracted when a compound medium from 110-d wastewater supernatant was used. The removal efficiencies of heavy metals from simulated electroplating wastewater were tested by using these prepared bioflocculants. The optimal conditions for heavy metal removal to BS-MBF were found to be at 374 mg/L at an initial pH of 6.0 and a contact time of 40 min. The adsorption capacities for Cu2+ and Zn2+ reached more than 90%, while for Cr6+ it reached approximately 30%. Overall, the study showed for the first time that wastewater supernatant from anaerobic co-digestion of corn straw and molasses wastewater can be used for producing bioflocculants, which can be effectively used to remove heavy metals from electroplating wastewater.