6,6'-Bis(chlorobenzoyl)-2,2'-dimethoxy-1,1'-binaphthyls 2a and 2b are prepared via P2O5-MsOH mediated regioselective diaroylation of 2,2'-dimethoxy-1,1'-binaphthyl (1). NiBr2/Zn-mediated aromatic coupling polymerization of 6,6-bis(chlorobenzoyl)-2,2'-dimethoxy-1,1'-binaphthyls 2 yields the corresponding wholly aromatic polyketones. When optically active bis(chlorobenzoylated) binaphthyls (2) are employed, optically active wholly aromatic polyketones 3 with large specific rotations, excellent thermal resistance, and excellent solubility to organic solvents are obtained.