A facile synthetic route toward functionalized 3-aryl-, 3, 3′-diaryl-, 3, 3′, 5-triaryl-4, 4′- dimethoxybiphenyls (polyphenyls) 3–5 with the terphenyl, quaterphenyl, quinquephenyl, and sexiphenyl skeleton starting from biphenyl-4, 4′-diol (1) in modest total yield is described. The route has been carried by the two transformations of the regioselective NBS (N-bromosuccinimide)-mediated bromination of 2 in MeCN at reflux and Suzuki–Miyaura ...