In this study, we report the novel energy behavior of high-performance nanostructured materials in a segmented thermoelectric micro-generator (TEG). Several physical elements of the materials must be considered to determine their behavior in the thermoelectric energy conversion: temperature dependence of material properties, geometric structure, segmentation, and the symmetry of each or both p-type and n-type nanostructure semiconductor thermoelements. Recently, many efforts have reported effects independent on the thermoelectric performance of semiconductor materials. In this work, exhaustive research on the performance of high-performance nanostructured materials in a segmented thermoelectric micro-generator (TEG) was carried out. Our results show the efficiency and output power of the TEG using the temperature-dependent model, i.e., a variable internal resistance for a load resistance of the system. Our approach allows us to analyze symmetrical and asymmetric geometries, showing maximum and minimum peaks values in the performance of the TEG for specific [Formula: see text] values. The performance of the TEG is improved by about [Formula: see text] and [Formula: see text], for efficiency, and output power, respectively, considering a trapezoidal geometric shape in the 2p-3n segmented system, compared with the conventional rectangular shape.