Scanning electrochemical microscopy (SECM) and scanning vibrating electrode technique (SVET) were used to investigate the electrochemical behaviour of the top surface of the 2098-T351 alloy welded by friction stir welding (FSW). The SVET technique was efficient in identifying the cathodic and anodic weld regions. The welding joint (WJ), which comprises the thermomechanically affected zone (TMAZ) and the stir zone (SZ), was cathodic relative to the heated affected zone (HAZ) and the base metal (BM). The reactivities of the welding joint at the advancing side (AS) and the retreating side (RS) were analyzed and compared using SECM technique in the competition mode by monitoring the dissolved oxygen as a redox mediator in 0.005 mol L−1 NaCl solution. The RS was more electrochemically active than the AS, and these results were correlated with the microstructural features of the welded alloy.