The synthesis and characterization of poly(monofluorenylacetylenes) obtained by polymerization of 2-ethynyl-9,9-bis[(S)-3,7-dimethyl-octyl]fluorene and 2-ethynyl-9,9-bis[(S)-2-methylbutyl]fluorene are described. The effect of the structure of the alkyl chain at the C(9) position of fluorene on the properties of the materials was studied by differential scanning calorimetry, thermogravimetric analysis, X-ray diffraction analysis, UV/Vis spectroscopy, photoluminescence, and circular dichroism. Polymerization of chiral 2-ethynylterfluorene functionalized with (S)-2-methylbutylalkyl chains was studied. The resulting polymer exhibits high thermal stability; its emission spectrum occurs in the violet-blue region and shows no significant red shift on passing from a solution to the solid state.