Biological reuse of spent sulfidic caustic (SSC) originating from oil refineries is a promising method for the petrochemical industry because of low handling cost. SSC typically contains high concentrations of sulfur, with the most dominant sulfur compounds being sulfide (S2−). SSC is also characterized by a high pH and elevated alkalinity up to 5–15% by weight. Because of these characteristics, SSC can be used for denitrification of NO3−-N in the biological nitrogen removal process as both the electron donor and buffering agent in sulfur-utilizing autotrophic denitrification. In this study, two kinds of SSC (SSC I, SSC II) produced from two petrochemical companies were used for autotrophic denitrification in a field-scale wastewater treatment plant (WWTP). The effluent total nitrogen (TN) concentration in this process was about 10.5 mg/L without any external carbon sources and the nitrification efficiency was low, about 93.0%, because of alkalinity deficiency in the influent. The injection of SSC I, but not SSC II, promoted nitrification efficiency, which was attributed to the difference in the NaOH/S ratio between SSC I and II. SSC was injected based on sulfide concentration of SSC required to denitrify NO3−-N in the WWTP. SSC I had higher NaOH/S than SSC II and thus could supply more alkalinity for nitrification than SSC II. On the other hand, additional TN removal of about 9.0% was achieved with the injection of both SSCs. However, denitrification efficiency was not proportionally increased with increasing SSC injection because of NO3−-N deficiency in the anoxic tank due to the limited capacity of the recycling pump. For the same reason, sulfate concentration, which is the end product of sulfur-utilizing autotrophic denitrificaiton in the effluent, was also not increased with increasing SSC injection.