Controlled‐Disorder Asymmetrical Donors Enable Efficient All‐Small‐Molecule Solar Cells with Excellent Solution‐Processability

All-small-molecule organic solar cells (all-SMOSCs) are promising candidates for next-generation photovoltaics owing to their well-defined molecular structures and excellent batch-to-batch reproducibility, yet their efficiency is limited by morphology control and processability. Here, we report three asymmetric small molecule donors-MPhS-HF, MPhS-OP, and MPhS-PF-engineered with distinct side-chain functionalities to systematically investigate the interplay between molecular design, solution-state interactions, crystallization kinetics, and blend morphology. Among them, MPhS-OP demonstrates delayed crystallization and favorable miscibility with the non-fullerene acceptor L8-BO, enabling the formation of finely interpenetrating network morphologies that facilitate efficient exciton dissociation, balanced charge transport, and suppressed recombination losses. As a result, binary MPhS-OP:L8-BO devices achieve a record power conversion efficiency of 18.12% under conventional spin-coating, along with exceptional processing tolerance, maintaining > 16.4% efficiency in thick-film, high-speed blade-coated, green solvent-processed, and large-area devices. In situ spectroscopy and thermodynamic modeling reveal that the superior performance arises from the distinct film-formation dynamics of MPhS-OP, which delays donor precipitation relative to L8-BO, suppressing premature phase segregation and ensuring reproducible nano-interpenetrating morphologies across processing conditions. This work establishes asymmetric small molecule donor design as a powerful strategy to couple molecular packing control with solution processability, offering a viable route toward scalable and high-performance all-SMOSCs.