Spiro polycyclic aromatic compounds have been known as rigid chiral scaffolds. In order to extend their applications, an efficient preparation route to enantiopure derivatives is highly required. Here, we design 10,10'-spirobi[indeno[1,2- b][1]benzothiophene]-7,7'-diol to achieve efficient optical resolution. The compound was successfully synthesized and resolved by chiral HPLC on a semipreparative scale. The absolute configuration of its enantiopure isomer was determined through single-crystal X-ray structure analysis of its derivative. The compound was also transformed into its derivatives with donor-acceptor (D-A) type systems. The obtained chiral D-A type molecules exhibited remarkable solvent-dependence fluorescence and were found to be solvent-sensitive circularly polarized luminescent materials. These results clearly demonstrated the utility of 10,10'-spirobi[indeno[1,2- b][1]benzothiophene]-7,7'-diol as a versatile building block for chiral spiro polycyclic aromatic compounds.