Dithieno[3,2‐b:2’,3’‐d]thiophene (DTT) derivative contains three annulated thiophene rings, which have attracted great attention in the field of materials due to its planar and conjugated molecular, structural rigidity, and increased solubility. Herein, the one‐step modular construction of a series of structurally well‐defined 2,6‐disubstituted dithieno[3,2‐b:2’,3’‐d]thiophenes (2,6‐DTT) involves Pd/Cu(I)‐catalyzed Sonogashira coupling and LiNH2‐mediated ring‐closing reaction with element sulfur was reported. The method allows the selective and straightforward introduction of different aryl substitution into DTT without otherwise tedious separation and purification processes. The preliminary study of the thermal and photophysical properties demonstrated that the introduction of substituent in phenyl has great impact for the parent molecule, which enable this protocol to synthesis high‐performance 2,6‐DTT through the different alkynes.