Electron affinity is one of the most important parameters that guide chemical reactivity. Halogens have the highest electron affinities among all elements. A class of molecules called superhalogens has electron affinities even greater than that of Cl, the element with the largest electron affinity (3.62 eV). Traditionally, these are metal-halogen complexes which need one electron to close their electronic shell. Superhalogens have been known to chemistry for the past 30 years and all superhalogens investigated in this period are either based on the 8-electron rule or the 18-electron rule. In this work, we have studied two classes of unconventional superhalogens: borane-based superhalogens designed using the Wade-Mingo’s rule that describes the stability of closo-boranes, and pseudohalogen based superhalogens. In addition, we have shown that superhalogens can be utilized to build hyperhalogens, which have electron affinities exceeding that of the constituent superhalogens, and also to stabilize unusually high oxidation states of metals.