Ternary ZnGeP2 with large capacity and suitable plateau is considered to be alternative anode for LIBs, while it suffers heavy-use of Ge raw-material inducing high cost-price thus failure of commercialization. Herein, a unique atomic substitution strategy is proposed by using Si-atom to totally replace Ge site in ZnGeP2. Interestingly, novel ZnSiP2 as twin-analogue is achieved, keeping the great advantages of high ICE (90 %), low plateau (∼0.35 V) and comparable rate performance (4000 mA/g, 629 mAh/g) for LIBs. More specially, such ZnSiP2 twin even exhibits higher thermo-stability (1046 vs 891 °C), larger capacity (1554 vs 1387 mAh/g) and lower voltage-hysteresis (0.28 vs 0.44 V) than ZnGeP2, which are unexpected and attractive for battery-safety and energy improvement. The above unusual phenomena are investigated in-detail, and the results show that owing to the similar radius and electronegativity between Si&Ge, the ZnSiP2 enables the same structural phase with ZnGeP2 matrix thus keeping its electrochemical advantages. Meanwhile, the ZnSiP2 exhibits larger formation energy (−1.24 eV) toward better structural-stability, lighter Si-component to higher capacity, lower Si-lithiated potential oriented smaller voltage-hysteresis, thus showing high performances in LiCoO2//ZnSiP2 full-cell. The above atomic substitution strategy can be easily extended to other good performance yet high cost electrode materials toward application.