We develop structure–property relations for organic field effect transistors using a polymer/small-molecule blend active layer. An array of bottom gate, bottom contact devices using a polymeric dielectric and a semiconductor layer of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT) is described and shown to have good device-to-device uniformity. We describe the nucleation and growth processes that lead to the formation of four structurally distinct regimes of the diF-TES-ADT semiconductor film, including evidence of layer-by-layer growth when spin-coated onto silver electrodes and an organic dielectric as part of a polymer blend. Devices exhibiting a maximum saturation mobility of 1.5 cm2 V−1 s−1 and maximum current modulation ratio (Ion/Ioff) of 1.20 × 105 are visualised by atomic force microscopy and appear to have excellent domain connectivity and aligned crystallography across the channel. In contrast, poorly performing devices tend to show a phase change in semiconductor crystallinity in the channel centre. These observations are enhanced by direct visualisation of the potential drop across the channel using Kelvin probe microscopy, which confirms the importance of large, well-aligned and well-connected semiconductor domains across the transistor channel.