Crystalline polymorphism of organic semiconductors is among the critical factors in determining the structure and properties of the resultant organic electronic devices. Herein we report for the first time a solvent-type-dependent polymorphism of a long fused-ring organic semiconductor and its crucial effects on charge transport. A new polymorph of 5,11-bis(triethylsilylethynyl)anthradithiophene (TES ADT) is obtained using solvent-assisted crystallization, and the crystalline polymorphism of TES ADT thin films is correlated with their measured hole mobilities. The best-performing organic thin film transistors of the two TES ADT polymorphs show subthreshold slopes close to 1 V dec(-1), and threshold voltages close to zero, indicating that the density of traps at the semiconductor-dielectric interface is negligible in these devices and the observed up to 10-fold differences in hole mobilities of devices fabricated with different solvents are largely resultant from the presence of two TES ADT polymorphs. Moreover, our results suggest that the best-performing TES ADT devices reported in the literature correspond to the new polymorph identified in this study, which involves crystallization from a weakly polar solvent (such as toluene and chloroform).