The O-arylation of o-enaminone functionalized phenols, namely, (E)-3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-ones, has been achieved via a self-promoted process in the presence of CuI, which provided a class of new biaryl ethers bearing a reactive enaminone fragment. The reactions were performed under mild conditions and the functionalized biaryl ether products have been found as useful building blocks for the assembly of heterocyclic compounds.