This study developed a novel chem-bio hybrid process using sulfurized micron zero-valent iron (S-ZVI) and biochar composite (S-ZVI@biochar) with dechlorinating bacteria (DB) and *Shewanella oneidensis* MR-1 for trichloroethylene (TCE) degradation. S-ZVI@biochar enhanced stability, biocompatibility, and TCE removal. The DB + MR-1 + S-ZVI@biochar system achieved 96.5% TCE removal after 30 days, 3.7 times higher than bare ZVI. Improved electron transfer efficiency, microbial community structure adjustment, and iron recycling contributed to this enhanced performance. S-ZVI@biochar facilitated electron transport, improving dechlorination capacity and showing promise for long-term TCE removal in anaerobic environments.
