The 1-(organoselanyl)perfluoroalkanols 1, 37 4, and 10 were successfully prepared and reactions with hexanoyl chlorides to produce the corresponding, esters 5, 7, and 8, accompanied by the selenoesters 6 were conducted. The DBU-mediated alkylations of the heptafluorobutanols 4, 10, and the alpha-p-nitrobenzoate 2 with alkyl halides easily provided alkyl phenyl selenides 9a-9i and 11a-11c in good to high yields.