We herein describe the synthesis of novel pentafluorinated tolane fluorophores, which possess an extended π-conjugated structure with a large molecular dipole moment along the longitudinal axis. We also report a detailed evaluation of both the photophysical and thermal behaviors of these fluorophores. All molecules displayed photoluminescence (PL) characteristics in both the crystalline state and in dilute solutions. The large longitudinal dipole moment induced solvatochromic PL behavior, which switched sensitively with changes in the solvent polarity. In addition, incorporation of the fluorinated tolane-based solid-state light-emitting moiety into the polymer side chain was found to be responsible for the PL characteristics observed in the solid state. It was also noteworthy that the polymerization protocol led to a significant enhancement in the thermal stability, with the thermal decomposition temperature increased by 90 °C. Accordingly, novel solid-state light-emitting materials with high thermal stabilities were successfully developed as promising candidates for use in light-emitting and optoelectronic applications.