A process for preparing polyphenylene ethers from monohydric phenols which have alkyl substituents in both ortho positions and possibly also in one meta position but not in the para position, by oxidative coupling with oxygen-containing gases in the presence of an oxidation catalyst and of an electrically conducting compound which counteracts the electrostatic charge in the reaction mixture, in organic solution, comprises using as electrically conducting compound a salt of a carboxamide derivative of the formula I ##STR1## or mixtures of such salts, where R.sup.1 is a saturated or singly or multiply unsaturated aliphatic group which can have a terminal phenyl group and which contains a total of 8-30 carbon atoms, it also being possible for these carbon atoms to be interrupted by isolated oxygen atoms,R.sup.2 is hydrogen or C.sub.1 -C.sub.4 -alkyl,A is an aliphatic, araliphatic or cycloaliphatic or aromatic bridge of up to 10 carbon atoms,n and m are each 1 to 3,Q.sup..sym. is ammonium, an alkali metal cation or the equivalent of an alkaline earth metal cation or a cation of a metal of groups IVb to VIIb of the periodic table.