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Chain elongation technology utilises microorganisms in anaerobic digestion to transform waste biomass into medium-chain fatty acids that have greater economic value. This innovative technology expands upon traditional anaerobic digestion methods, requiring abundant substrates that serve as electron donors and acceptors, and inoculating microorganisms with chain elongation functions. While this process may result in the production of by-products and elicit competitive responses, toxicity suppression of microorganisms by substrates and products remains a significant obstacle to the industrialisation of chain elongation technology. This study provides a comprehensive overview of existing research on widely employed electron donors and their synthetic reactions, competitive reactions, inoculum selection, toxicity inhibition of substrates and products, and increased chain elongation approaches. Additionally, it presents actionable recommendations for future research and development endeavours in this domain, intending to inspire and guide researchers in advancing the frontiers of chain elongation technology. [Display omitted] • Multiple pathways for synthesizing MCFAs were systematically presented. • The types of electron donors and inoculum usually employed in the chain elongation were reviewed. • The principle of chain elongation inhibition by substrates and products was outlined. • Methods to enhance the chain elongation were evaluated, future research avenues were presented. [ABSTRACT FROM AUTHOR]