In this study we synthesized a series of solution-processable small molecules comprising 2,2′-bithiophene (BTh), terthiophene (TTh), and thiobarbituric acid (TB) units as the central core, π-conjugated spacer, and acceptor end-capping moieties, respectively, but with alkyl side-chains of different lengths presented from their central BTh units (TBTThBTh-H, TBTThBTh-C4, TBTThBTh-C8, TBTThBTh-C12). We then investigated the structure–property relationships of these compounds in terms of their packing behaviors and bulk heterojunction (BHJ) photovoltaic properties. And we found that the packing of these molecules in neat films is critically dependent of their side-chain lengths, as evidenced by the variations in their lamellar structures determined with grazing-incidence wide-angle X-ray scattering (GIWAXS). The power conversion efficiencies (PCEs) of the photovoltaic BHJ devices comprising these small molecules and PC₆₁BM exhibited zigzag-shaped variations with respect to the alkyl side-chain lengths, with the PCE of devices incorporating TBTThBTh-H and TBTThBTh-C8 being higher than those of devices incorporating TBTThBTh-C4 and TBTThBTh-C12. Using GIWAXS to probe the molecular packing in the BHJ active layers, we found that the alkyl chain lengths of the small molecules had a large impact on the formation of crystallites in the BHJ films; the molecules with more uniform and shorter alkyl side-chain lengths provide stronger intermolecular interactions, being more favorable for the crystallization of these molecules.