A family of trialkylsilylethynyl (TAS)-functionalized pentacenes (PENs) and anthradithiophenes (ADTs) are of immense interest due to their good solubility and air stability for uses in optoelectronic devices. Different TAS-substituted PENs and ADTs would result in different crystal packing motifs and carrier transport properties. Quantum nuclear-enabled hopping model combined with molecular dynamics (MD) simulations was used to investigate the effects of the chemical modifications on the carrier transport properties. The disorder-free hole mobilities show that 6,13-bis(trialkylsilylethynyl)anthradithiophenes (TAS-ADTs) own better intrinsic hole transport behaviors than 6,13-bis(trialkylsilylethynyl)pentacenes (TAS-PENs). The MD simulations show that in comparison with TAS-PENs, the thermal disorder effects are less significant for TAS-ADTs; this is probably due to the C–H···S hydrogen bonds, which are thought to stabilize the molecules in crystal environments. Furthermore, the syn-TAS-ADTs show more serio...