Dibenzo crown ether-substituted units of fluorene and acene-bearing copolymers have been successfully synthesized. FTIR, 1H and 13C NMR spectroscopy, DSC, TGA and GPC were used to characterize the resulting copolymers (P1-P5). With fascinating quantum yield, the polymers showed large band gaps. With a polydispersity index of 1.58-2.21, these polymers showed a higher mol. weight (16,080-20,480). Strong thermal stability was indicated by DSC and TGA studies. The cyclic voltammetry anal. found that these polyfluorenes were stable in the range of 0.43-0.53 eV under redox conditions with HOMO and LUMO. For light-emitting materials, thermal stability and emission studies display strong results that are desirable.