Currently, non-fullerene-based acceptors in organic solar cells (OSCs) have gained significant attention of researchers owing to their particular characteristics. Herein, new W-shaped dithiophene based acceptor chromophores (D1-D8) possessing A-π-D-π-A configuration were fabricated via end group structural tailoring by utilizing promising acceptors groups. To probe the effect of end group manipulation on the optoelectronic properties of entitled chromophores, density functional theory/time-dependent density functional theory (DFT/TD-DFT) calculations were accommodated at B3LYP/6–311 G(d,p) functional. Frontier molecular orbitals (FMOs) findings revealed that the derivatives (D1-D8) exhibited narrow band gap (1.191–2.110 eV) than that of reference chromophore (R=2.380 eV) due to efficient acceptor moieties. UV–Vis data collected in chloroform solvent revealed that λmax values of D1-D8 were existed in visible region (738.6–692.5 nm). Moreover, D2 and D4 proves to be the best chromophores exhibiting least band gap of 1.191 and 2.000 eV and broad absorption spectrum i.e., 738.573 and 735.986 nm, respectively. Among all the designed compounds, D2, D3, D4 and D6 manifested higher open circuit voltage values. Theoretical analysis disclosed that all the designed molecules exhibited almost comparable results with each other. Nevertheless, D2 and D4 provided significant findings and can be utilized as best candidate for use in optoelectronic devices.