In this work, hardwood sulfite spent liquor (HSSL)—a by-product from a pulp and paper industry—was used as substrate to produce short-chain organic acids (SCOAs) through acidogenic fermentation. SCOAs have a broad range of applications, including the production of biopolymers, bioenergy, and biological removal of nutrients from wastewaters. A continuous stirred tank reactor (CSTR) configuration was chosen to impose selective pressure conditions. The CSTR was operated for 88 days at 30 °C, without pH control, and 1.76 days of hydraulic and sludge retention times were imposed. The culture required 46 days to adapt to the conditions imposed, reaching a pseudo-steady state after this period. The maximum concentration of SCOAs produced occurred on day 71—7.0 g carbon oxygen demand (COD)/L that corresponded to a degree of acidification of 36%. Acetate, propionate, butyrate, valerate, and lactate were the SCOAs produced throughout the 88 days, with an average proportion of 59:17:19:1.0:4.0%, respectively.