There is disclosed a process for preparing polyhalogenated carbinols having formula: ##STR1## by reacting a compound having formula: ##STR2## with a system consisting of a compound having formula: ##STR3## and of a divalent metal or of a metal salt, in protic dipolar solvents, in which formulaeR=H, an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkadienyl, phenyl, naphthyl, anthracyl group, a heterocyclic radical, optionally substituted;R'=H, a haloalkyl, --CN, --COOR" group with R" equal to H or to an alkyl group;X.sup.1 =Cl, Br; =X.sub.2 =F, Cl, Br;X.sup.3 =Cl, Br, CF.sub.3, CCl.sub.3 ; Y=Br or Cl when X.sup.1, X.sup.2 and X.sup.3 are different from Br.