Herein,6,-dinaphtho[2,1-b:2′,1′-f ]thieno [3,2-b]thiophene (5H-21DNTT)-a solution-processable derivative of DNTT-was characterized and studied for its potential as a crystalline solution-processed organic semiconductor to achieve high mobility and stable organic thin-film transistor (OTFT) operation. The performance of a bottom-gate, bottomcontact OTFT with a 5H-21DNTT semiconductor was analyzed with different polymeric organic gate dielectrics via various solution-processed techniques. In comparison to other polymeric gate dielectrics, Parylene C exhibited a superior performance for 5H-21DNTT OTFT devices, and the OTFT devices showed a remarkable average mobility of 10.9 cm 2 V -1 s -1 , as well as a maximum mobility exceeding 15 cm 2 V −1 s −1 , with a 100% reliability factor.In recent years, organic thin-film transistors (OTFTs) have been extensively studied in the pursuit of achieving low-cost, large-area, and flexible electronics. [1][2][3] Owing to the unique properties of organic semiconductors (OSCs), OTFTs are potential candidates for realizing future display applications, [4,5] large-area sensor arrays, [6,7] gas and biochemical sensors, [8][9][10] and radio-frequency identification (RFID) tag applications. [11,12] The solution processability of OSCs is the most promising parameter to facilitate low-cost mass production of novel device applications via printing techniques on flexible and large-area substrates. [13][14][15][16]