Both crystal packing and molecular size have strong influences on the charge mobility for organic semiconductors. The crystal structures for oligothiophene (nT) can be roughly classified into two types: the Z = 2 (two molecules in one unit cell) or high temperature (HT) phase and the Z = 4 or low temperature (LT) phase. Through first-principles calculations within the Marcus electron transfer theory coupled with random walk simulation for room temperature charge diffusion constants, we found that the hole mobility of the HT phase is about 3–4 times larger than that of the LT phase because the molecular packing in the HT phase favors the hole transfer (i.e., the frontier orbital wave function phases of the dimer are constructive, which tends to maximize the overlap), while for the LT phase, the molecules are packed in a position that reduces the intermolecular orbital overlap due to phase cancellation. As the molecular size increases from 2T to 8T, the hole mobility tends to increase because the reorganiza...