Syntheses of 2,2'-bisalcoholic group-substituted 9,9'-spirobifluorene monomers 2 were performed by the reaction of 2,2'-dihydroxy-9,9'-spirobifluorene 2a with haloalcohols. Polycarbonates consisting of 9,9'-spirobifluorene skeleton in the main chain (PC 4) were synthesized by the polycondensation of 2,2'-bisalcoholic monomers 2 and triphosgene or diphenyl carbonate. PC 4 showed good thermal stability: the 5% weight loss temperature was over 330 C under both nitrogen and air atmospheres. The glass transition temperature was in a range of 16-269 degrees C estimated by differential scanning calorimetry, depending on the flexibility of the alkylene or oxyethylene chains of 2. PC 4 showed high solubility toward ordinary organic solvents such as CHCl3, benzene, and THF, making possible the preparation of the flexible thin films. Very high refractive index in a range of 1.62-1.66 at 589 nm was observed although PC 4 consists only of C, H, and 0 atoms, whereas very low degree of birefringence was confirmed. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3658-3667, 2010