Oligo(2,5-bis(3-dodecylthiophen-2-yl)thieno[3,2-b]thiophene)s Tn and Tn-2CN (n = 4, 8, 12, 20, n represents the number of thiophene rings), which have H and CN end-groups, respectively, were synthesized, and the effect of chain-length and end-groups on their properties was studied. For both Tn and Tn-2CN, a red-shift of absorption spectra was observed as the chain length increased. Introduction of electron-withdrawing CN end-groups resulted in a remarkable red-shift of absorption spectra in both solution and film states for shorter oligomers (n = 4 and 8). However, for oligomers with n = 12 and 20, obvious red-shift of absorption spectra was only observed in the film state. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) energy levels were both lowered by introducing CN end-groups, and the level of reduction decreased with an increase of the chain length. Both the chain length and end-groups influenced the thin film microstructures of the oligomers as revealed by two-dimensional grazing incidence X-ray diffraction (2D-GIXD) and atomic force microscopy (AFM) studies. The oligomers with n = 4 and 8 stood on the substrates with a tilt angle, and the films of T4-2CN and T8-2CN were characterized with 3D crystal structures. In contrast, the oligomers with n = 12 and 20 adopted an edge-on arrangement with the long axes of the molecules parallel to the substrates, like polymeric counterparts. Compared to the films of T12 and T20, those of T12-2CN and T20-2CN comprised larger and more oriented crystal-domains to the substrates along with shorter lamellar distances. Charge-transport properties of the oligomers were influenced by both the chain length and end-groups due to their remarkable effect on the film morphology and packing structures. The film of T8-2CN combined three features: large domain sizes, low surface-roughness and diminished grain boundaries, and therefore exhibited the highest field-effect mobility.