In contrast to the multi-cation case, experimental investigations of genuine multi-anion materials for optoelectronic energy conversion are much more sparse. There has been some experimental work on certain oxynitrides (e.g., LaTiO 2 N, TaON ), oxysulfides (e.g., Y 2 Ti 2 O 5 S 2 , oxyhalides (e.g., BiOI ) and sulfoiodides (e.g., SbSI ). However, very few multi-anion materials have been explored and their PV efficiencies are generally below 5%. In this Perspective, we will discuss the prospects of multianion and polyanionic phosphosulfides (PSs) as potential high-quality semiconductors. We will see that PSs are still nearly unexplored in the context of optoelectronic energy conversion. Nevertheless, most of the known PS materials feature band gaps in the visible, crystal structures with threedimensional bonding networks, and a remarkable degree of chemical diversity that is not easily matched by other inorganic material families. The fundamental reason for their chemical versatility is the wide range of oxidation states that phosphorus can take in the simultaneous presence of a more electropositive element (a metal) and a more electronegative one (sulfur). The implications for the discovery of optoelectronic semiconductors are intriguing. In fact, it is already possible to identify PSs with direct band gaps in the visible and low carrier effective massespotential indicators of high α and high μwhen phosphorus is both in its maximum (+5) and minimum (-3) oxidation state. We will conclude this Perspective by proposing an approach for the high-throughput synthesis of known and hypothetical PS compounds in thin-film form.