Advances in the field of frustrated Lewis pair (FLP) chemistry have led to the discovery of radical pairs, obtained by a single-electron transfer (SET) from the Lewis base to the Lewis acid. Radical pairs are intriguing for their potential to enable cooperative activation of challenging substrates (e.g., CH₄, N₂) in a homolytic fashion, as well as the exploration of novel radical reactions. In this review, we will cover the two known mechanisms of SET in FLPs—thermal and photoinduced—along with methods (i.e., CV, DFT, UV-vis) to predict the mechanism and to characterise the involved electron donors and acceptors. Furthermore, the available techniques (i.e., EPR, UV-vis, transient absorption spectroscopy) for studying the corresponding radical pairs will be discussed. Initially, two model systems (PMes₃/CPh₃⁺ and PMes₃/B(C₆F₅)₃) will be reviewed to highlight the difference between a thermal and a photoinduced SET mechanism. Additionally, three cases are analysed to provide further tools and insights into characterizing electron donors and acceptors, and the associated radical pairs. Firstly, a thermal SET process between LiHMDS and [TEMPO][BF₄] is discussed. Next, the influence of Lewis acid complexation on the electron acceptor will be highlighted to facilitate a SET between (pBrPh)₃N and TCNQ. Finally, an analysis of sulfonium salts as electron acceptors will demonstrate how to manage systems with rapidly decomposing radical species. This framework equips the reader with an expanded array of tools for both predicting and characterizing SET events within FLP chemistry, thereby enabling its extension and application to the broader domain of main-group (photo)redox chemistry.