The convergent synthesis of a series of acceptor–donor–acceptor (A-D-A) type dicaynovinyl (DCV)-substituted oligoselenophenes DCVnS (n = 3–5) is presented. Trends in thermal and optoelectronic properties are studied, in dependence on the length of the conjugated backbone. Optical measurements reveal red-shifted absorption spectra and electrochemical investigations show lowering of the lowest unoccupied molecular orbital (LUMO) energy levels for DCVnS compared to the corresponding thiophene analogs DCVnT. As a consequence, a lowering of the bandgap is observed. Single crystal X-ray structure analysis of tetramer DCV4S provides important insight into the packing features and intermolecular interactions of the molecules, further corroborating the importance of the DCV acceptor groups for the molecular ordering. DCV4S and DCV5S are used as donor materials in planar heterojunction (PHJ) and bulk-heterojunction (BHJ) organic solar cells. The devices show very high fill factors (FF), a high open circuit voltage, and power conversion efficiencies (PCE) of up to 3.4% in PHJ solar cells and slightly reduced PCEs of up to 2.6% in BHJ solar cells. In PHJ devices, the PCE for DCV4S almost doubles compared to the PCE reported for the oligothiophene analog DCV4T, while DCV5S shows an about 30% higher PCE than DCV5T.