Oxidative biaryl coupling reaction of phenol ether derivatives with the hypervalent iodine reagent, phenyliodine (III) bis (trifluoroacetate)(PIFA), in the presence of BF3· Et2O gave a variety of substituted biphenyl and binaphthyl compounds in high yields. Replacement of PIFA with a more practical polymer-supported hypervalent iodine reagent has also been achieved.