Polypyrrole (PPy) is a conducting polymer with attractive thermoelectric (TE) properties. It is simple to fabricate and modify its morphology for enhanced electrical conductivity. However, such improvement is still limited to considerably enhancing TE performance. In this case, a single-wall carbon nanotube (SWCNT), which has ultrathin diameters and exhibits semi-metallic electrical conductivity, might be a proper candidate to be combined with PPy as a core shell one-dimensional (1D) nanocomposite for higher TE power generation. In this work, core shell nanocomposites based on SWCNT/PPy were fabricated. Various amounts of pyrrole (Py), which are monomer sources for PPy, were coated on SWCNT, along with methyl orange (MO) as a surfactant and ferric chloride as an initiator. The optimum value of Py for maximum TE performance was determined. The results showed that the SWCNT acted as a core template to direct the self-assembly of PPy and also to further enhance TE performance. The TE power factor, PF, and figure of merit, zT, values of the pure PPy were initially recorded as ~1 µW/mK² and 0.0011, respectively. These values were greatly increased to 360 µW/mK² and 0.09 for the optimized core shell nanocomposite sample. The TE power generation characteristics of the fabricated single-leg module of the optimized sample were also investigated and confirmed these findings. This enhancement was attributed to the uniform coating and good interaction between PPy polymer chains and walls of the SWCNT through π–π stacking. The significant enhancement in the TE performance of SWCNT/PPy nanocomposite is found to be superior compared to those reported in similar composites, which indicates that this nanocomposite is a suitable and scalable TE material for TE power generation.