The invention provides alkene fluoroalkanol and fluorinated polyol precursors to fluoroalkanol-substituted .alpha.,.beta.-unsaturated esters. The fluoroalkanol-substituted .alpha.,.beta.-unsaturated esters are olefins that can be readily polymerized to provide fluoroalkanol-substituted polymers useful in lithographic photoresist compositions. Also provided are methods for synthesizing the alkene fluoroalkanol and fluorinated polyol precursors.