In-situ Raman spectroscopy is implemented for the first time to monitor dynamic charge transfer processes at polarisable interfaces between two immiscible electrolyte solutions (ITIES) in real time. A custom-designed new electrochemical cell is described which allows probing the Raman signals of ferroin ions as a function of the potential applied across the water|1,2-dichlorobenzene (DCB) interface. This approach is also used for investigating the heterogeneous electron transfer reaction involving dimethylferrocene in DCB and potassium hexacyanoferrate (II/III) in the aqueous phase. The evolution of the Raman signals during potentiodynamic measurements is recorded in real-time with a resolution of a few seconds. ; Junta de Castilla y Leon (GR71, BU349-U13) and Ministerio de Economia y Competitividad (CTQ2010-17127) is gratefully acknowledged. D.I. thanks Ministerio de Economia y Competitividad for his predoctoral FPI fellowship. D.P. and D.J.F. acknowledge financial support from the EPSRC (grant EP/K007025/1)