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Two second-phases with an opposite potential difference to the α-Mg matrix may affect the discharge mechanism of magnesium (Mg) anodes for primary Mg-air cells through different micro-galvanic behaviors. Herein, using Mg-Ca-xSn alloys anode with Mg2Ca and CaMgSn phases, we investigated their influence on the dissolution mode of Mg-anode during discharge state via in-situ scanning vibrating electrode technique (SVET) technology. Firstly, the peak surface positive potential of Mg-1Ca alloy only containing Mg2Ca phase and Mg-1Ca-1Sn alloy with CaMgSn/Mg2Ca phase increases multiplied by 10 during the discharge process compared to that of OCP, exhibiting accelerated anodic substrate dissolution. Moreover, Mg2Ca-phases can be attacked firstly while promoting the discharge of the α-Mg matrix surrounding them, leading to the preferential dissolution of grain boundaries and “chunk effects (CE)” occurrence. More CaMgSn/α-Mg couples are activated to form dispersed micro-galvanic cell islands, which also boosts the dissolution of the α-Mg matrix but reduces the area of high-intensity dissolution reaction due to CaMgSn acting as a cathode. However, excessive CaMgSn-phase generally fails to discharge effectively to reduce anode efficiency, although it can improve the self-peeling capacity of the film layer through physical detachment; in addition, with Sn content increasing to 3wt.%, the open circuit voltage of Mg-1Ca-3Sn significantly declines. Mg-1Ca-0.2Sn exhibits the highest cell voltage and anodic efficiency by introducing a tiny amount of dispersed short rod-like CaMgSn, due to the adjusted dissolution mode, enhanced electrochemical activity and inhibited CE. Finally, our study provides a universal mechanism for fabricating Mg-anode with high performance via phase composition modulation.