The performance of organic field-effect transistors (OFETs) significantly depends on the properties of the interface between the semiconductor and gate dielectric. Here, we study the impact of chemically modified and morphologically controlled dielectrics on the performance of poly(2,5-bis(3-alkylthiophen-2-yl)thieno[3,2-b]thiophene) (pBTTT) semiconductors. We find that the molecular packing, domain size, and carrier mobility of pBTTT are highly sensitive to dielectric chemistry and dielectric roughness. The large and well-oriented terraced domains that are the origin of pBTTT's high performance can develop well on certain dielectrics, but can be disrupted on others.