Semiconducting single-walled carbon nanotubes (s-SWCNTs) with large diameters are highly desired in the construction of high performance optoelectronic devices. However, it is difficult to selectively prepare large-diameter s-SWCNTs since their structure and chemical stability are quite similar with their metallic counterparts. In this work, we use SWCNTs with large diameter as a raw material, conjugated polymer of regioregular poly-(3-dodecylthiophene) (rr-P3DDT) with long side chain as a wrapping agent to selectively separate large-diameter s-SWCNTs. It is found that s-SWCNTs with a diameter of ~1.9 nm are effectively enriched, which shows a clean surface. By using the sorted s-SWCNTs as a channel material, we constructed thin-film transistors showing charge-carrier mobilities higher than 10 cm2V−1s−1and on/off ratios higher than 103.