A correlation between the hole transport and corresponding structural properties of the bulk regioregular poly(3âhexylthiophene) (rrâP3HT) is studied as a function of temperature by the timeâofâflight (TOF) and wide angle Xâray diffraction (WAXD) techniques. The thermallyâreversible structural evolution along the (100) and (020) directions in a semiâcrystalline rrâP3HT can be divided into two distinct temperature regions. At T > 120 °C, a large thermal expansion along the ÏâÏ stacking direction in the nanocrystals and a deteriorated ordering in the material result in negative slopes of temperature and electric field dependences of hole mobility. The WAXD data suggest that the hole transport is limited by a decrease in the crystallinity and by an increase in the hopping distance along the ÏâÏ stacking direction, while the Gaussian Disorder Model (GDM) with temperatureâindependent parameters cannot be applied. At T < 120 °C, the transportârelated structural changes are negligible and the temperature and electric field dependences of hole mobility can be described by the GDM with constant energetic (Ï âŒ 120 meV) and positional disorder parameters (ÎŁ ⌠3.33). These values suggest that the hole transport is limited by the amorphous phase, as commonly seen in disordered polymers. Moreover, a regiorandom P3HT (rraâP3HT), which shows a temperatureâindependent intermolecular distance of âŒ15.3Ă
, provides a route for separate examination of the amorphous phase in rrâP3HT.