Three new octyloxy substituted spirobifluorenes, 2,7-diphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DPBSBF, 1a), 2,7-dibiphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DBBSBF, 1b) and 2,7-diterphenyl-3′,6′-bis(octyloxy)-9,9′-spirobifluorene (DTBSBF, 1c) were prepared. All the compounds had been fully characterized by 1H and 13C NMR, UV–Vis, DSC, mass spectrometry and gave satisfactory elemental analyses. They possessed good solubility in common organic solvents and good homogeneous film formation. The optical energy band gap of DBBSBF was 3.27eV between the HOMO energy level, 5.85eV, measured by UPS and the LUMO, 2.58eV, calculated from absorption spectrum. A blue organic light emitting diode (OLED) based on the structure of ITO/TPD (60nm)/DBBSBF (40nm)/Alq3 (20nm)/LiF (1nm)/Al (100nm) showed good performance. The luminance of 3125cd/m2 was observed at a drive voltage of 12.8V and the colour coordinate in CIE chromaticity was (0.14, 0.12). The external quantum efficiency was obtained to be 2.8% at 100cd/m2.