A new series of α-functionalized trichloromethylcarbinols have been synthesized from corresponding α-halomethyl ketones, esters, and amides in 48-78% overall yields. Reactivity of nitrates obtained in the first step was dependent on the electron-withdrawing nature of the functional groups, and increases with increasing electron deficiency. Synthetic applications of such trichloromethylcarbinols for the preparation of chloromethyl-α-diketones, trichloromethylated dihydrofurans, and enol acetates of α-functionalized acid chlorides have been demonstrated. The reaction of these compounds in the Jocic-Reeve reaction was also demonstrated.