Many studies have proven the significant roles of side chains far beyond being the solubilizing groups as well as the interesting merits of fluorination on pi-backbones in the intrinsic properties and device performances of organic semiconductors. Considering the integration of the two features, we herein introduce a 4,4,4-trifluorobutyl (CF3- terminated) side chain into a 2H-1,2,3-benzotriazole-core-based acceptor-donor-acceptor-donor-acceptor-type non-fullerene acceptor (NFA) named YCF3 and demonstrate its effectiveness in optoelectronic, morphological, and photovoltaic properties. Comparative experimental and theoretical studies confirmed the unique features of YCF3 (e.g., red-shifted film absorption, better absorptivity, finely adjusted energies, and higher mobility) associated with its enhanced crystalline nature, compared with its analogous NFA with an n-butyl side chain named YCH3. The best power conversion efficiency (PCE) of 18.21% is achieved in a YCF3-based binary organic solar cell (OSC) together with good heat and light stability. Moreover, a YCF3-based OSC presents a remarkable PCE of 16.11% in an inverted-structure large-area device.