We successfully developed and applied an electron bombardment technique on the generation of anionic species by using matrix isolation method recently. Several anionic systems were produced and characterized with their IR features. These anionic systems belong to (1) hypervalent species and/or (2) free radicals which are all exceptions of the octet rule and require specific bonding models to describe. Our study combining experimental and theoretical works will provide more insights into chemical bonding of these species.