Recently, there has been growing interest in the implementation of various "catalysts" to further diversify the substrate scope for inverse vulcanization reactions. While there have been several proposals on the mechanism of how these catalysts work, the speciation of sulfur in these mixtures has remained elusive. As a key component to understanding when and if these catalysts are appropriate, we sought to elucidate the role of dithiocarbamate species in inverse vulcanization reactions by attempting to characterize the speciation of sulfur. The reaction efficacy for various substrates containing different functional groups with sulfur, either with or without a metal dithiocarbamate, potassium diethyldithiocarbamate (K-DTC), suggests the formation of a rapidly fluctuating sulfur speciation and, most importantly, the presence of anionic sulfur. The work concludes with some suggestions on best practices for the utilization of dithiocarbamate catalysts based on our results.