Single-walled carbon nanotubes (SWNTs) have been widely used as leading additives for improving the thermoelectric properties of organic materials, due to their unique structure and excellent electronic transport properties. However, the as-synthesized SWNTs are mixtures (mix-SWNT) of semiconducting (sc-SWNT) and metallic (met-SWNT) carbon nanotubes. The significantly different surface character and transport behavior of sc-SWNT and met-SWNT frequently raise the difficulty of modifying microstructures, and tuning transport properties of SWNTs/organic composites, when using mix-SWNTs as dispersion phase. Herein, we prepared high quality sc-SWNTs/rr-P3DDT composite film by presorting pure sc-SWNT from the raw mix-SWNTs using regioregular poly(3-dodecylthiophene) (rr-P3DDT). Both the smoothness and compactness of sc-SWNTs/rr-P3DDT are great improved, as compared with the mix-SWNTs/rr-P3DDT films, and the sc-SWNTs are well-dispersed and uniformly wrapped by rr-P3DDT with diameter less than 50 nm. The significantly enhanced Seebeck coefficients and power factors are obtained in the sc-SWNT/rr-P3DDT samples. As the result, the maximum power factor of 60 μW/mK2 in 50 wt% sc-SWNTs sample is 70% higher than that of mix-SWNTs/P3DDT sample. This work reveals the effectiveness of pure semiconductor SWNTs as fillers to optimize the thermoelectric properties of CNT/polymer nano-composites.