A new confined p-phenylenevinylene (PPV)-type polymer (BPAF-PPV) has been synthesized using Wittig condensation. The chemical structure of the polymer was well defined by (1)H-NMR, (13)C-NMR, and FT-IR spectroscopic analysis. BPAF-PPV contains oligomeric PPV units separated by hexafluoroisopropylidene groups in the main chain; it is fully soluble in common organic solvents and has a number-average molecular weight of 4570 g mol(-1). Differential scanning calorimetry indicates that BPAF-PPV is amorphous and displays a glass transition temperature of 114 degrees C. The optical properties of the polymer were investigated by UV-visible absorption and photoluminescence spectroscopies. Its thin film showed a blue photoluminescence with a narrow emission spectrum. A high photoluminescence quantum efficiency of about 83% was determined in dilute solution. From the cyclic voltammetry analysis, the electrochemical bandgap was estimated to be 3.08 eV. A single-layer diode device of the configuration indium-tin oxide/BPAF-PPV/aluminium has been fabricated and has a relatively low turn-on voltage of 3.0 V.