Configurationally bistable defects can exist in either of two different structural configurations for the same charge state. Each configuration exhibits distinct optical and electronic properties. Here a framework is presented for the use and interpretation of deep level capacitance transient spectroscopy measurements in the study of these defects. Examples are presented for the MFe center in InP, a bistable A‐center‐related defect in Si, and the EL2 center in GaAs.