Several fluoroalcohols have been prepared by the free-radical addition of methanol, ethanol and isopropanol to such fluoro-olefins as C3F6, CFH˭CF-CF3, (CF3)zCFCF˭CFCF3and H(CF2)4CF˭CF2. Proper experimental conditions for their synthesis are described. Owing to their strong tendency to form hydrogen bonds, fluoroalcohols are excellent solvents for polymeric materials which possess receptive sites for hydrogen bonding formation. The solvent power of the fluoroalcohols on some polar polymers, mostly aliphatic polyamides, has been tested. 2,2,3,4,4,4-Hexafluorobutanol (HFB) shows the best solvent ability among compounds of this class. Its properties and solvent power have been evaluated and compared to those of trifluoroethanol (TFE) and hexafluoroisopropanol (HFIP).