Low-molecular-mass organoboron quinoline-8-thiolate and -selenolate complexes as model compounds, and organoboron polymers incorporated their complex structures into the poly(p-phenylene-ethynylene) main chain were prepared. Tetracoordination states of boron atoms in the obtained compounds were confirmed by B-11 NMR spectroscopy, and the detailed structures of the model compounds were determined by single-crystal X-ray diffraction analysis. The polymers were synthesized by Sonogashira-Hagihara coupling reaction of organoboron quinolate-based monomers having diiodo groups with 1,4-diethynylbenzene derivatives bearing electron-donating or -withdrawing groups in moderate yields. Their optical properties were studied by UV-vis absorption and photoluminescence spectroscopies. Increasing atomic number of the 16 Group atom adjacent to the boron atom caused emission shift to longer wavelength and decreasing of absolute quantum yields for both the model compounds and the polymers. There are no differences between the polymers with the donating pi-conjugated linker and with the accepting one in the photoluminescence property, resulting from efficient energy transfer from pi-conjugated main chain to Q ligand. Furthermore, the obtained polymers showed high refractive indices (n(d) > 1.66).