Abstract A series of new substituted triphenylamine (TPA) derivatives with alkyl thieno[3,2- b]thiophene and thiophene units were synthesized in a combinatorial manner. Suzuki coupling of a dioxaborolane TPA derivative and 2-bromo-3-nonylthieno[3,2- b]thiophene or Stille coupling of fresh stannyl thieno[3,2- b]thiophene was used. All compounds were characterized by 1H and 13C NMR, HRMS, UV–vis spectrometry and DSC measurements. It was demonstrated that the optical and thermal properties of these materials can be tuned by varying both the conjugation length and thienothiophene and thiophene combination on the TPA branches. Moreover, the measured molar extinction coefficients were increasing from 63,000 ( λ max = 354 nm) to 131,000 L mol −1 cm −1 ( λ max = 428 nm) for TPA-thienothiophenes and TPA-bithiophene thienothiophenes, respectively. Some of them showed molecular glass behavior.