The issue of energy supply for wireless sensors is becoming increasingly severe with the advancement of the Fourth Industrial Revolution. Thus, this paper proposed a thermoelectric self-powered wireless sensor that can harvest industrial waste heat for self-powered operations. The results show that this self-powered wireless sensor can operate stably under the data transmission cycle of 39.38 s when the heat source temperature is 70 °C. Only 19.57% of electricity generated by a thermoelectric power generation system (TPGS) is available for use. Before this, the power consumption of this wireless sensor had been accurately measured, which is 326 mW in 0.08 s active mode and 5.45 μW in dormant mode. Then, the verified simulation model was established and used to investigate the generation performance of the TPGS under the Dirichlet, Neumann, and Robin boundary conditions. The minimum demand for a heat source is cleared for various data transmission cycles of wireless sensors. Low-temperature industrial waste heat is enough to drive the wireless sensor with a data transmission cycle of 30 s. Subsequently, the economic benefit of the thermoelectric self-powered system was also analyzed. The cost of one thermoelectric self-powered system is EUR 9.1, only 42% of the high-performance battery cost. Finally, the SEPIC converter model was established to conduct MPPT optimization for the TEG module and the output power can increase by up to approximately 47%. This thermoelectric self-powered wireless sensor can accelerate the process of achieving energy independence for wireless sensors and promote the Fourth Industrial Revolution.