The integrated system of microbial electrosynthesis (MES) coupled with chain elongation has been considered a promising platform for carboxylic acids production. However, this biotechnology is still in its infancy, and many limitations are needed to be transcended, such as low electron transfer efficiency between cathode and microbes. In this study, nano zero-valent iron (NZVI) was employed to improve carboxylic acid production in the integrated system, and the promotion mechanisms were revealed. Results suggested that the highest production concentrations of acetate, butyrate, and caproate were observed at 7.5 g/L optimized NZVI dosage, increasing the total yield and coulomb efficiency by 23.7 % and 40.3 % compared to the control. Mechanism studies indicated that the hydrogen and electron released by the anaerobic corrosion of NZVI could be used as additional reducing equivalents, thereby enhancing the electron transfer performance. Besides, NZVI was also proven to facilitate the formation of electroactive biofilms according to the results of biofilm characterization and total DNA. In functional microbes' respect, the moderate NZVI enriched the chain elongator in biofilm, like Clostridium_sensu-stricto_12, and upregulated the activities of key enzymes of homoacetogenesis and chain elongation metabolic pathways, like carbon-monoxide dehydrogenase and hydroxyacyl-CoA dehydratase. This study provided the evidence and revealed how NZVI assisted carboxylic acid production from CO2 via chain elongation in MES. Display omitted •NZVI anaerobic corrosion devoted additional electron for chain elongation.•Biofilm redox capacity was enhanced by attached NZVI and aged NZVI particles.•NZVI facilitated biofilm shaping with homoacetogenic and chain-elongating bacteria.•Microbial distribution was regulated in response to different NZVI dosages.•Moderate NZVI upregulated the key enzymes expression related to WL and RBO pathways.