The interface between dielectric and organic semiconductor is critically important in determining organic thin-film transistor (OTFT) performance. Surface polarity of the dielectric layer can hinder charge transport characteristics, which has restricted utilization of polymeric dielectric materials containing polar functional groups. Herein, the electrical characteristics of OTFTs are analyzed depending on the alkyl chain length of organic semiconductors and surface polarity of polymer dielectrics. High-performance dibenzothiopheno[6,5-b:6 & PRIME;,5 & PRIME;-f]thieno[3,2-b]thiophene (DBTTT) and newly synthesized its alkylated derivatives (C6-DBTTT and C10-DBTTT) are utilized as organic semiconductors. As dielectric layers, non-polar poly(1,3,5-trimethyl-1,3,5-trivinylcyclitrisiloxane) (pV3D3) and poly(2-cyanoethyl acrylate-co-diethylene glycol divinyl ether) [p(CEA-co-DEGDVE)] with polar cyanide functionality are utilized. The fabricated OTFTs with pV3D3 commonly exhibit the excellent charge transport characteristics. In addition, the OTFT performance is improved with lengthening the alkyl chain in organic semiconductors, which can be attributed to the molecular orientation of semiconductors. On the other hand, non-alkylated DBTTT OTFTs with polar p(CEA-co-DEGDVE) show relatively poor electrical characteristics, while their performance is drastically enhanced with the alkylated DBTTTs. The ultraviolet photoelectron spectroscopy (UPS) reveals that surface polarity of the dielectric layer can be abated with alkyl chain in organic semiconductors. It is believed that this study can provide a useful insight to optimize dielectric/semiconductor interface to achieve high-performance OTFTs.