mobility. [18] However, P-OSCs have a drawback in batch-to-batch reproducibility of donor polymers, which potentially limits the mass deployment of OSCs. [19] Compared to P-OSCs, small-molecule based OSCs (SM-OSCs) are more attractive in commercialization because of well-defined molecular structures, [20][21][22] simpler synthesis and purification, [23][24][25] and low batch-to-batch variations. [26][27][28][29] With the SM donors developed, the state-of-the-art SM-OSCs show similar PCEs as those obtained for P-OSCs (over 11%) using fullerene derivative, PCBM, as the electron acceptor. [19,[30][31][32][33] However, when the NFSM acceptors were used in nonfullerene-based small molecule organic solar cells (NFSM-OSCs) their PCE can only reach slightly over 10% [34][35][36][37] which is much lower than those obtained for nonfullerene polymer solar cells (NFP-OSCs) with usually PCE over 13%. [38,39] The progress of NFSM-OSCs is strongly lagged behind their polymer counterparts.The PCE of an OSC is determined by three parameters, opencircuit voltage (V oc ), short-circuit current density (J sc ), and fill factor (FF). The main reason for the low PCE in NFSM-OSCs is due to their relative low J sc and FF. [40,41] As shown in Table S1 (Supporting Information), all of the efficient NFP-OSCs with PCE over 14% show high J sc (>20 mA cm −2 ) and high FF In this paper, two near-infrared absorbing molecules are successfully incorporated into nonfullerene-based small-molecule organic solar cells (NFSM-OSCs) to achieve a very high power conversion efficiency (PCE) of 12.08%. This is achieved by tuning the sequentially evolved crystalline morphology through combined solvent additive and solvent vapor annealing, which mainly work on ZnP-TBO and 6TIC, respectively. It not only helps improve the crystallinity of the ZnP-TBO and 6TIC blend, but also forms multilength scale morphology to enhance charge mobility and charge extraction. Moreover, it simultaneously reduces the nongeminate recombination by effective charge delocalization. The resultant device performance shows remarkably enhanced fill factor and J sc . These result in a very respectable PCE, which is the highest among all NFSM-OSCs and all small-molecule binary solar cells reported so far.