Five novel spiro[benzo[c]fluorene-7,9'-fluorene] based dyes, including 5-[spiro[benzo[c]fluorene-7,9'-fluoren]-5-yl] spiro[benzo[c]fluorene-7,9'-fluorene] (7), 5-[spiro[benzo[c]fluorene-7,9'-fluoren]-9-yl] spiro[benzo[c]fluorene-7,9'-fluorene] (8), 5-[spiro[benzo[c]fluorene-7,9'-fluoren]-2'-yl] spiro[benzo[c]fluorene-7,9'-fluorene] (9), 9-[spiro[benzo[c]fluorene-7,9'-fluoren]-9-yl] spiro[benzo[c]fluorene-7,9'-fluorene] (10), and 2'-[spiro[benzo[c]-fluorene-7,9'-fluoren]-2'-yl] spiro[benzo[c]fluorene-7,9'-fluorene] (11) were successfully prepared from the corresponding halogen and boronic acid derivatives through the Suzuki coupling reaction, respectively. Chemical structures were confirmed by $^1H$ nuclear magnetic resonance (NMR), $^{13}C$ NMR, Fourier transforminfrared spectrscopy, mass spectroscopy, and elemental analysis. The thermal properties were determined by differential scanning calorimetry and thermal gravimetric analysis. The relationships between the optical and electrochemical properties and the combined positions between these dimers were systematically investigated using UV-vis, photoluminescence (PL), and photoelectron spectroscopy. These five dimers exhibited high fluorescent quantum yields and good morphological stability with high glass transition states > $174^{\circ}C$. Dimer 7 showed a UV absorbance peak at 353 nm, emission PL peak at 424 nm, and quantum efficiency of 0.62 in a cyclohexane solution.