Conjugated polymers and small molecules based on alternating electron-donating (D) and electron-accepting (A) building blocks have led to state-of-the-art organic solar cell materials governing efficiencies beyond 10%. Unfortunately, the connection of D and A building blocks via cross-coupling reactions does not always proceed as planned, which can result in the generation of side products containing D-D or A-A homocoupling motifs. Previous studies have reported a reduced performance in polymer and small molecule solar cells when such defect structures are present. A general consensus on the impact of homocouplings on device performance is, however, still lacking as is a profound understanding of the underlying causes of the device deterioration. For differentiating the combined effect of molecular weight and homocouplings in polymer solar cells, a systematic study on a small molecule system (DTS(FBBTh2)2) is presented. The impact of homocouplings on nanomorphology, thermal, and electro-optical properties is investigated. It is demonstrated that small quantities of homocouplings (