The aim of this study was to develop a mathematical model to assess the effect of soluble microbial products production and external carbon source addition on the performance of a sulfur-driven autotrophic denitrification (SdAD) process. During SdAD, the growth of autotrophic biomass (AUT) was accompanied by the proliferation of heterotrophic biomass mainly consisting of heterotrophic denitrifiers (HD) and sulfate-reducing bacteria (SRB), which are able to grow on both the SMP derived from the microbial activities and on an external carbon source. The process was supposed to occur in a sequencing batch reactor to investigate the effects of the COD injection on both heterotrophic species and to enhance the production and consumption of SMP. The mathematical model was built on mass balance considerations and consists of a system of nonlinear impulsive differential equations, which have been solved numerically. Different simulation scenarios have been investigated by varying the main operational parameters: cycle duration, day of COD injection and quantity of COD injected. For cycle durations of more than 15 days and a COD injection after the half-cycle duration, SdAD represents the prevailing process and the SRB represent the main heterotrophic family. For shorter cycle duration and COD injections earlier than the middle of the cycle, the same performance can be achieved increasing the quantity of COD added, which results in an increased activity of HD. In all the performed simulation even in the case of COD addition, AUT remain the prevailing microbial family in the reactor.