High productivity and specificity in anaerobic digesters arise because complex microbiomes organize into a metabolic cascade to maximize energy recovery and to utilize the advantage that the gaseous end product methane freely bubbles out of the system. These lessons were applied to ascertain whether a reactor microbiome could be shaped to produce a different end product. The liquid product n-caproic acid was chosen, which is a 6-carbon-chain carboxylic acid that is valuable and that has a relatively low maximum solubility concentration for product recovery. Acetoclastic methanogenesis was inhibited by pH control and a route was provided for n-caproic acid extraction by implementing selective, in-line recovery. Next, ethanol was supplemented to promote chain elongation, which is a pathway in which short-chain carboxylic acids are elongated sequentially into medium-chain carboxylic acids with two-carbon units derived from ethanol. The reactor microbiome developed accordingly with the terminal process catalyzed by chain-elongating bacteria. As a result, n-caproic acid production rates increased to levels comparable to anaerobic digestion systems for solid waste treatment.