Nonfullerene-based organic solar cells (OSCs) have made a huge breakthrough in the recent years. Introducing a proper side chain on the pi-conjugated backbone plays a vital role for further improving the power conversion efficiency (PCE) of OSCs due to easy tuning of the physical properties of the molecule such as absorption, energetic level, solid-state stacking, and charge transportation. More importantly, the side chain significantly affected the blend films morphology and thus determined the PCEs of the devices. In this work, two low-band-gap nonfullerene acceptors, ATT-4 and ATT-5, with an alkyl or branched alkyl substitute on indacenodithiophene (IDT) and thieno[3,4-b]thiophene (TbT) backbone were synthesized for investigating the effect of the substituent on the performance of the nonfullerene acceptors (NFAs). In comparison to ATT-1 with p-hexylphenyl-substituted IDT and n-octyl-substituted TbT moieties, ATT-4 and ATT-5 exhibit better crystallinity with shorter interchain distance and ordered molecular structure in neat and the corresponding blend films. The tailored ATT-5 exhibits a high PCE of 12.36% with a V-oc of 0.93 V, J(sc) of 18.86 mA cm(-2), and fill factor (FF) of 0.71, blending with a wide-band-gap polymer donor PBDB-T. Remarkably, although ATT-4 and ATT-5 exhibit broader light absorption, the devices obtained higher V-oc than that of ATT-1 mainly due to the reduced nonradiative recombination in the blend films. These results implied that side-chain engineering is an efficient approach to regulate the electronic structure and molecular packing of NFAs, which can well match with polymer donor, and obtain high PCEs of the OSCs with improved V-oc, J(sc), and FF, simultaneously.