A convenient process for the manufacture of alkoxylated derivatives of PFPE alcohols is herein provided. The process envisages the use of a boron-based catalyst and an iodine source and is characterized in that a PFPE alkoxide is prepared separately, contacted with a boric acid triester of the same PFPE alcohol and finally submitted to alkoxylation in the presence of an iodine source. The process allows achieving an alkoxylation degree of at least 2 with high yields and under conditions that are convenient on an industrial scale.