Harnessing energy lost in the form of heat is an important challenge today. Organic thermoelectric materials (TE) can convert lost heat into electricity at relatively low temperature. Single-walled carbon nanotubes (SWCNTs) are known to boost the TE properties of organic-based materials at room temperature (TR). However, the TE performance decreases with the increasing temperature, which restricts the working temperature region of the devices. Here, we present a three steps investigation: initially, the influence of the net of SWCNTs on TE properties of polymer matrix; secondly, creation of hybrid fillers via SWCNTs treatment with gold chloride; lastly, chemical post-treatment of obtained systems in the temperature range 325–410 K. In the process of HAuCl4 aerosolization (gold chloride treatment) on the surface of nanotubes, different ionic conformations (Au and AuCl4−) can be formed. For this reason, we performed a theoretical investigation on the influence of ionic conformations on SWCNTs on the electronic structure. Implementation of SWCNTs net into polymer matrix alongside gold chloride doping and chemical post-treatment successfully increased the power factor of the system in the temperature interval from 300 to 410 K. These results demonstrate the potential of combined approach in creation of hybrid fillers based on organic/inorganic materials with chemical post-treatment in boosting the thermoelectric performance within the whole operating temperature of polymer-based composite alongside the importance of theoretical modeling in tuning the electronic structure of composite systems through a material-by-design approach.