Thermoelectric (TE) materials can directly convert heat into electrical energy. However, they sustain costly production procedures and batch-to-batch performance variations. Therefore, developing scalable synthetic techniques for large-scale and reproducible quality TE materials is critical for advancing TE technology. This study developed a facile, high throughput, solution-chemical synthetic technique. Microwave-assisted thermolysis process, providing energy-efficient volumetric heating, was used for the synthesis of bismuth and antimony telluride (Bi2Te3, Sb2Te3). As-made materials were characterized using various techniques, including XRPD, SEM, TEM, XAS, and XPS. Detailed investigation of the local atomic structure of the synthesized Bi2Te3 and Sb2Te3 powder samples was conducted through synchrotron radiation XAS experiments. Radial distribution functions around the absorbing atoms were reconstructed using reverse Monte Carlo simulations, and effective force constants for the nearest and distant coordination shells were subsequently determined. The observed differences in the effective force constants support high anisotropy of the thermal conductivity in Bi2Te3 and Sb2Te3 in the directions along and across the quintuple layers in their crystallographic structure. The as-made materials were consolidated via Spark Plasma Sintering to evaluate thermal and electrical transport properties. The sintered TE materials exhibited low thermal conductivity, achieving the highest TE figure-of-merit values of 0.7 (573 K) and 0.9 (523 K) for n-type Bi2Te3 and p-type Sb2Te3, respectively, shifted significantly to the high-temperature region when compared to earlier reports, highlighting their potential for power generation applications. The scalable, energy- and time-efficient synthetic method developed, along with the demonstration of its potential for TE materials, opens the door for a wider application of these materials with minimal environmental impact.