Designing giant-molecule acceptors is deemed as an up-and-coming strategy to construct stable organic solar cells (OSCs) with high performance. Herein, two giant dimeric acceptors, namely, DYV and DYFV, have been designed and synthesized by linking two Y-series derivatives with a vinyl unit. DYFV exhibits more red-shifted absorption, down-shifted energy levels, and enhanced intermolecular packing than DYV because the intramolecular noncovalent interaction (H···F) of DYFV leads to better coplanarity of the backbone. The D18:DYFV film owns a distinct nanofibrous nanophase separation structure, a more dominant face-on orientation, and more balanced carrier mobilities. Therefore, the D18:DYFV OSC achieves a higher photoelectron conversion efficiency of 17.88% and a longer-term stability with a