"Molecule-framework" and "side-chain" engineering is powerful for the design of high-performance organic semiconductors. Based on 2DQTTs, the relationship between molecular structure, film microstructure, and charge-transport property in organic thin-film transistors (OTFTs) is studied. 2DQTT-o-B exhibits outstanding electron mobilities of 5.2 cm(2) V-1 s(-1), which is a record for air-stable solution-processable n-channel small-molecule OTFTs to date.