The morphological structure of poly(3-hexylthiophene) (P3HT) thin films deposited by both Matrix Assisted Pulsed Laser Evaporation (MAPLE) and solution spin-casting methods are investigated. The MAPLE samples possessed a higher degree of disorder, with random orientations of polymer crystallites along the side-chain stacking, - stacking, and conjugated backbone directions. Moreover, the average molecular orientations and relative degrees of crystallinity of MAPLE-deposited polymer films are insensitive to the chemistries of the substrates onto which they were deposited; this is in stark contrast to the films prepared by the conventional spin-casting technique. Despite the seemingly unfavorable molecular orientations and the highly disordered morphologies, the in-plane charge carrier transport characteristics of the MAPLE samples are comparable to those of spin-cast samples, exhibiting similar transport activation energies (56 vs. 54 meV) to those reported in the literature for high mobility polymers. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 39-48