The thermoelectric application is one of most popular energy harvesting application from waste heat. The thermoelectric generators, thermoelectric coolers, and thermoelectric modular devices criterion comes in both sustainable energy as well as renewability of electrical energy from waste heat sinks. The recovery operations are optimized with the help of modeling using MATLAB software. The material science based thermoelectric applications can be modeled with the help of MATLAB simulink modeling. The numerical and algorithmic method of MATLAB modeling is for the development of hybrid thermoelectric coolers and generators (solar thermoelectric generators, radiative cooler, heat sinks). Later, the use of MATLAB software gives opportunities to develop the cost effective and high power thermoelectric generators. The emerging commercial device making is also discussed for thermoelectric generator using MATLAB optimization.