The rail transit in sulfate-rich areas faces the combined effects of stray current and salt corrosion; however, the sulfate ion transport and concrete degradation mechanisms under such conditions are still unclear. To address this issue, novel sulfate transport and mesoscale splitting tests were designed, with a focus on considering the differences between the interfacial transition zone (ITZ) and cement matrix. Under the influence of stray current, the ITZ played a pivotal role in regulating the transport and mechanical failure processes of sulfate attack, while the tortuous and blocking effects of aggregates almost disappeared. This phenomenon was termed the “stray current-induced ITZ effect.” The experimental data revealed that the difference in sulfate ion transport attributed to the ITZ ranged from 1.90 to 2.31 times, while the difference in splitting strength ranged from 1.56 to 1.64 times. Through the real-time synchronization of splitting experiments and microsecond-responsive particle image velocimetry (PIV) technology, the mechanical properties were exposed to the consequences of the stray current-induced ITZ effect. The number of splitting cracks in the concrete increased, rather than along the central axis, which was significantly different from the conditions without stray current and the ideal Brazilian disk test. Furthermore, a sulfate ion mass transfer model that incorporates reactivity and electrodiffusion was meticulously constructed. The embedded finite element calculation exhibited excellent agreement with the experimental results, indicating its reliability and accuracy. Additionally, the stress field was determined utilizing analytical methods, and the mechanism underlying crack propagation was successfully obtained. Compared to the cement matrix, a stray current led to more sulfates, more microstructure degradation, and greater increases in thickness and porosity in the ITZ, which was considered to be the essence of the stray current-induced ITZ effect.