Winery effluents containing high ethanol concentrations and diverse organic matter are ideal substrates for producing medium-chain carboxylic acids via fermentation and chain elongation. However, the process needs to be better understood. This study presents novel insights into the bioconversion mechanisms of medium-chain carboxylic acids by correlating fermentation and chain elongation kinetic profiles with the study of microbial communities at different pH (5 to 7) conditions and temperatures (30 to 40°C). It was found that high productivities of MCCA were obtained using a native culture and winery effluents as a natural substrate. Minor pH variations significantly affected the metabolic pathway of the microorganisms for MCCA production. The maximal productivities of hexanoic (715mg/L/d) and octanoic (350mg/L/d) acids were found at pH 6 and 35°C. Results evidence that the presence of Clostridium, Bacteroides, and Negativicutespromotes the high productions of MCCA. The formation of heptanoic acid was favor when Mogibacterium and Burkholderia were present.