A heptagonal isomerized bithiophene imide (iBTI) acceptor has been effectively synthesized on a gram scale. Its series of β-, α',β-, α,α'-, α,α',β-, and α,α',β,β'-substituted derivatives can be obtained by controlling brominated sites. Single-crystal analyses indicate that the torsion angle of the imide backbone depends on the number and rigidity of β-substituted groups. Furthermore, the helical chirality of tetrasubstituted and [7]helicene-like derivatives based on iBTI shows great promise for the construction of chiral semiconductor materials.