Development of the convenient method for the synthesis of (hydroxyphenyl)perfluoro-alkylmethanols was achieved by the Meerwein-Ponndorf-Verley (MPV) type reduction of the in situ-generated perfluoroalkylated ketones as the key step. The benzylic OH group of the resultant alcohols was successfully converted to H or Rf(CH₂)_nO by way of the corresponding chlorides, this transformation being not easy by any other methods.