AbstractSpin-coating has been used extensively in the fabrication of electronic devices; however, the effects of the processing parameters have not been fully explored. Here, we systematically characterize the effects of the spin-coating time on the microstructure evolution during semiconducting polymer solidification in an effort to establish the relationship between this parameter and the performances of the resulting polymer field-effect transistors (FETs). We found that a short spin-coating time of a few seconds dramatically improve the morphology and molecular order in a conjugated polymer thin film because the π-π stacking structures formed by the polymer molecules grow slowly and with a greater degree of order due to the residual solvent present in the wet film. The improved ordering is correlated with improved charge carrier transport in the FETs prepared from these films. We also demonstrated the effects of various processing additives on the resulting FET characteristics as well as on the film drying behavior during spin-coating. The physical properties of the additives are found to affect the film drying process and the resulting device performance.