A portable vacuum interface allowing direct probing of the electrode-electrolyte interface was developed. A classical electrochemical system consisting of a gold working electrode, platinum counter electrode, platinum reference electrode, and potassium iodide electrolyte was used to demonstrate real-time observation of the gold iodide adlayer on the electrode and chemical species as a result of redox reactions using cyclic voltammetry (CV) and time-of-flight secondary ion mass spectrometry (ToF-SIMS, a vacuum-based surface technique) simultaneously. This microfluidic electrochemical probe provides a new way to investigate the surface region with adsorbed molecules and the region of the diffused layer with chemical speciation in liquids in situ by surface sensitive techniques.