Efficient organic electronic devices are fabricated from both small molecules and disperse polymers, but materials with characteristics in between remain largely unexplored. Here, we present a gram-scale synthesis for a series of discrete n-type oligomers comprising alternating naphthalene diimide (NDI) and bithiophene (T2). Using C-H activation, discrete oligomers of type T2-(NDI-T2)_n (n ≤ 7) and persistence lengths up to ∼10 nm are made. The absence of protection/deprotection reactions and the mechanistic nature of Pd-catalyzed C-H activation allow one to produce symmetrically terminated species almost exclusively, which is key to the fast preparation, high yields, and the general success of the reaction pathway. The reaction scope includes different thiophene-based monomers, end-capping to yield NDI-(T2-NDI)_n (n ≤ 8), and branching at T2 units by nonselective C-H activation under certain conditions. We show how the optical, electronic, thermal, and structural properties depend on oligomer length along with a comparison to the disperse, polymeric analogue PNDIT2. From theory and experiments, we find that the molecular energy levels are not affected by chain length resulting from the strong donor-acceptor system. Absorption maxima saturate for n = 4 in vacuum and for n = 8 in solution. Linear oligomers T2-(NDI-T2)_n are highly crystalline with large melting enthalpies up to 33 J/g; NDI-terminated oligomers show reduced crystallinity, stronger supercooling, and more phase transitions. Branched oligomers and those with bulky thiophene comonomers are amorphous. Large oligomers exhibit similar packing characteristics compared to PNDIT2, making these oligomers ideal models to study length-structure-function relationships at constant energy levels.