This review provides an insight into the chain-elongation technology for the production of caproic acid, a chemical widely used in the food, pharmaceutical, and cosmetic industries, from lactic acid in waste organic matter. The evolution of the technology is traced, the reaction mechanism is elucidated, and the properties of key microbial agents capable of carrying out the chain-elongation technology are summarized and compared, including pure bacterial isolates and reactor-mixed microorganisms. Furthermore, the parameters that regulate caproic acid formation by influencing microbial activity, competitive pathways, product selection, and carbon flow distribution, such as pH, temperature, electron donor, electron acceptor, and hydrogen partial pressure, are highlighted and discussed. It is worth noting that various caproic acid product extraction technologies were also summarized and assessed. Finally, based on the perspective of interdisciplinary field, bold suggestions for the future research direction are put forward.