The vast amount of waste heat released into the environment, from body heat to factories and boilers, can be exploited for electricity generation. Thermoelectrics is a sustainable clean energy solution that converts a heat flux directly into electrical power and vice versa and therefore has the potential for both energy harvesting and cooling technologies. However, the usage of thermoelectrics for large-scale applications is restrained by its device topologies and energy conversion cost efficiency trade-offs. The increase in complex topological designs reported in literature shows a shift towards customizability and improvement of thermoelectric devices for maximum energy conversion efficiency. Increasing design complexity will require an innovative, cost-effective fabrication method with design freedom capabilities. In light of this, this review paper seeks to summarize various thermoelectric topological designs as well as how 3D Printing technology can be a solution to the fabrication of cost-and performance-efficient thermoelectric devices. Specifically, as a process category of 3D Printing technology, Materials Jetting will be elaborated for its usefulness in the fabrication of thermoelectric devices. With in-depth research in materials jetting of thermoelectrics, the gap between small-scale materials research and scaled-up industry applications for energy harvesting through thermoelectric devices is expected to be bridged.