The pursuit of techniques with a high time resolution together with molecular signature information at the electrochemical interfaces has never stopped in order to explicitly monitor and understand the dynamic electrochemical processes. Here, we developed a transient electrochemical surface-enhanced Raman spectroscopy (TEC-SERS) to monitor the structural evolution of surface species at a time resolution that equals the transient electrochemical methods (e.g., cyclic voltammetry and chronoamperometry), so that the Raman signal with the molecular signature information and the electrochemical current signal can be precisely correlated. The technique was employed to study the redox process of nile blue on Ag surfaces. We revealed an interesting two-rate constant process and a peculiar increase of the absolute intensity during the reduction of nile blue on the Ag surface, which both related to the dissociation of nile blue aggregates and the follow-up reduction. Therefore, we were able to uncover the processes that are impossible to observe by conventional steady state SERS methods. The ability to provide a time resolution shorter than the charging time of the double layer capacitance with molecular fingerprint information has unprecedented significance for investigation of both reversible and irreversible electrochemical processes.