Nonvalence states of neutral molecules (Rydberg states) play important roles in nonadiabatic dynamics of excited states. In anions, such nonadiabatic transitions between non-valence and valence states have been much less explored even though they are believed to play important roles in electron capture and excited state dynamics of anions. The aim of this Feature Article is to provide an overview of recent experimental observations, based on time-resolved photoelectron imaging, of valence to nonvalence and nonvalence to valence transitions in anions and to demonstrate that such dynamics may be common-place in the excited state dynamics of molecular anions and cluster anions.