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The depth profiling of the element content and precipitation phase distribution of the AA4045/AA3003mod (Al-1.5Mn-0.35Cu alloy)/AA4045 brazed sheets were investigated by optical microscope observation, electron probe microanalysis (EPMA), focused ion beam-scanning transmission electron microscopy (FIB-STEM). The electrochemical test and sea water acetic acid test (SWAAT) were performed to obtain the evolution of electrochemical responses and corrosion forms of brazed sheet. EPMA results showed that a diffusion layer with the thickness of approximately 50 μm existed between the clad layer and core layer, where the Cu diffused from the core layer and Si diffused from the clad layer. It was found that brazing led to a significant low elements solid solution area at the end of the Si diffusion path, where the open circuit potential was lower by 25 mV comparing to the unaffected region. Thus the diffusion zone can provide effective cathodic protection to the unaffected region as sacrificial anode by the potential gradient. The SWAAT analysis revealed the corrosion mechanism of the residual cladding was pitting and intergranular corrosion. This area with high density of intermetallic compounds and Si particles increased sensitivity to localized attacks. These results demonstrated the successful application of the FIB-STEM system in illustrating the electrochemical responses and corrosion propagation by an accurate in-depth characterization of intermetallic particles and the matrix solid solution.