We investigate the effects of environmental conditions on the electrical stability of spin-coated 5,11-bis(triethylsilylethynyl)anthradithiophene (TES-ADT) thin-film transistors (TFTs) in which crosslinked poly(4-vinylphenol-co-methyl methacrylate) (PVP-co-PMMA) was utilized as a gate insulator layer. Atomic force microscopy observations show molecular terraces with domain boundaries in the spin-coated TEST-ADT semiconductor film. The TFT performance was observed to be superior in the ambient air condition. Under negative gate-bias stress, the TES-ADT TFTs showed a positive threshold voltage shift in ambient air and a negative threshold voltage shift under vacuum. These results are explained through a chemical reaction between water molecules in air and unsubstituted hydroxyl groups in the cross-linked PVP-co-PMMA as well as a charge-trapping phenomenon at the domain boundaries in the spin-coated TES-ADT semiconductor.