Hydrogen sulfide (H2S) is an important biological mediator involved in a wide array of physiological processes. Much of this activity is associated with the often-inseparable roles of reactive sulfur species, including persulfides (RSS–), polysulfides (HSn–), and related molecules. In addition, emerging examples of reactive selenium species, including H2Se, play complementary and often more potent roles in biological redox chemistry. Many of these small molecule bioregulators are known to interact with bioinorganic metal targets, although the fundamental chemistry of such systems remains underdeveloped, in part due to the lack of suitable methods to prepare and investigate such systems. As a first step toward bridging this gap, we recently reported examples of isolated persulfide, thiosulfide, thioselenide, and perselenide molecules, (1) as well as early examples of metal persulfide motifs (2). This presentation will focus on our recent work aimed at further probing the chemistry of redox active and inert metal persulfides, as well as hybrid S/Se metal species. Examples include Zn and Co persulfide complexes and associate reactivities with other small molecule S and Se motifs. We will also include recent work on further understanding the role of hybrid S/N small molecule bioregulators, such as SNO– and SSNO– (3) including work with Fe-based platforms, highlighting the formation of metal nitrosyl complexes with these platforms.