The crystallinity and intermolecular interaction among small molecules are enhanced in order to achieve reasonable phase segregation between the donor and acceptor in all-small-molecule organic solar cells (ASM OSCs). By substituting an alkyl side chain with a chlorine (Cl) atom on the original benzodithiophene terthiophene rhodanine (BTR) molecule, the new small molecular donor, namely BTR-Cl, processes a more ordered liquid crystalline property, down-shifted molecular energy levels, and higher crystallinity. When blended with a non-fullerene acceptor Y6, which has a complementary absorption profile and well-matched energy levels but no liquid crystalline property, a prominent phase separation and optimal film morphology are obtained. As a result, a record-high power conversion efficiency (PCE) of 13.6% is achieved, taking a large step forward in ASM OSCs. Our results highlight the importance of crystallinity to phase separation, suggesting the great promise of liquid crystalline materials in OSCs.