The stereoregularity effect on carrier mobility of stereoregular poly(N-vinylcarbazole) (PVK) was studied using metal–insulator–semiconductor charge extraction by the linearly increasing voltage technique. The hole mobility of stereoregular PVK thin film was dependent upon the stereoregularity (mm) and was enhanced to be 4.02 × 10−6 cm2 V−1 s−1 at mm = 94%, which was 4.8 times higher than that at mm = 50%. Furthermore, the activation energy depending on the stereoregularity of PVK was evaluated to be from 118 meV (mm = 50%) to 111 meV (mm = 94%) in faint variation. The enhanced carrier transport in the stereoregular PVK thin film was discussed by taking the stereoregularity involved with the intramolecular interaction through the carbazole substituents into consideration.