Molecular orientation and π–π stacking of nonfullerene acceptors (NFAs) determine its domain size and purity in bulk-heterojunction blends with a polymer donor. Two novel NFAs featuring an indacenobis(dithieno[3,2-b:2ʹ,3ʹ-d]pyrrol) core with meta- or para-alkoxyphenyl sidechains are designed and denoted as m-INPOIC or p-INPOIC, respectively. The impact of the alkoxyl group positioning on molecular orientation and photovoltaic performance of NFAs is revealed through a comparison study with the counterpart (INPIC-4F) bearing para-alkylphenyl sidechains. With inward constriction toward the conjugated backbone, m-INPOIC presents predominant face-on orientation to promote charge transport. The as-cast organic solar cells (OSCs) by blending m-INPOIC and PBDB-T as active layers exhibit a power conversion efficiency (PCE) of 12.1%. By introducing PC71BM as the solid processing-aid, the ternary OSCs are further optimized to deliver an impressive PCE of 14.0%, which is among the highest PCEs for as-cast single-junction OSCs reported in literature to date. More attractively, PBDB-T:m-INPOIC:PC71BM based OSCs exhibit over 11% PCEs even with an active layer thickness over 300 nm. And the devices can retain over 95% of PCE after storage for 20 days. The outstanding tolerance to film thickness and outstanding stability of the as-cast devices make m-INPOIC a promising candidate NFA for large-scale solution-processable OSCs.