Achieving efficient bulk-heterojunction (BHJ) solar cells from blends of solution-processable small-molecule (SM) donors and acceptors has proven particularly challenging due to the complexity in obtaining a favorable donor-acceptor morphology. In this report, we examine the BHJ device performance pattern of a set of analogous, well-defined SM donors -DR3TBDTT (DR3), SMPV1, and BTR -used in conjunction with the SM acceptor IDTTBM. Our examinations show that the nonfullerene "All-SM" BHJ solar cells made with DR3 and IDTTBM can achieve power conversion efficiencies (PCEs) of up to ca. 4.5% (avg. 4.0%) when the solution-processing additive 1,8diiodooctane (DIO, 0.8% v/v) is used in the blend solutions. The figures of merit of optimized DR3:IDTTBM solar cells contrast with those of "as-cast" BHJ devices from which only modest PCEs <1% can be achieved. Combining electron energy loss spectrum (EELS) analyses in scanning transmission electron microscopy (STEM) mode, carrier transport measurements via "metalinsulator-semiconductor carrier extraction" (MIS-CELIV) methods, and systematic recombination This article is protected by copyright. All rights reserved. 3 examinations by light-dependence and transient photocurrent (TPC) analyses, we show that DIO plays a determining role -establishing a favorable lengthscale for the phase-separated SM donoracceptor network and, in turn, improving the balance in hole/electron mobilities and the carrier collection efficiencies overall.