Novel organoboron polymers containing pyrazaboles in the main chain were prepared by Heck-Sonogashira coupling. The coupling reaction between diyne monomers and pyrazabole derivatives gave the corresponding polymers in good yields. The number-average molecular weights of the obtained polymers were relatively high compared with the organoboron polymers prepared by hydroboration polymerization. The obtained polymers were further investigated by UV-vis absorption and fluorescence spectroscopy.