It is a challenge to achieve high output power of the thermoelectric generator (TEG) for high-temperature waste heat recovery due to the working fluids with low thermal conductivity (such as air) or low tolerance of temperature (water or oil). In this paper, the gallium-based liquid metal (LM) with a high boiling point (>1000 ℃) and thermal conductivity (>20 W/mK) are introduced to significantly enhance heat charging and discharging at the hot/cold sides of TEG. We also developed an electromagnetic induction pumping method for the effective LM-driven flow at high temperatures. A three-dimensional coupling multi-parameter optimization simulation model of LM-based TEG was developed to reveal the internal heat transfer and power generation mechanism for clarifying the impact factors of the performance. The results have shown that the power generation capacity can be effectively improved by increasing the inlet temperature (Thot-in). It is worth noting that the temperature difference (ΔT) of the TEG module is severely limited by the thermal resistance (Rcapacity) of the LM heat capacity, such as, when the flow rate of 2 L/min, the Rcapacity accounts for 90.6 % (0.020 ℃/W). It is easier to achieve a larger open circuit voltage by increasing the height of the thermoelectric leg, but the Pmax is constantly weakened. Compared with Xceltherm 600 and Solar salt, LM heat transfer fluid has more obvious advantages in enhancing the power generation performance of the system. The LM-based TEG experiment platform was established to study heat transfer and power generation characteristics. The results have demonstrated that good consistency was proved by comparing experimental and numerical data. And the Pmax of the LM-based TEG system is 0.16 W/cm2 at ΔT of 136 ℃. LM-based TEG can open new perspectives for broad applications in high-temperature waste heat recovery.