Species selective spectroelectrochemistry (SSSE) is described by relating the derivative absorbance (dA/dt) signals with electrochemical currents for conventional transient electrochemical experiments. Expressions relating the currents with the dA/dt signals were obtained. From these expressions, physical constants such as coefficients and molar absorptivities of electrogenerated species can be determined. By obtaining both derivative absorbance and current signals concurrently and comparing them, one can perform the SSSE experiments. The utility of the SSSE in sorting out electrochemical information is demonstrated.