C2-Symmetric 9,9′-spirobifluorenes with 2,2′-, 3,3′-, and 4,4′-dihydroxyls were conveniently prepared from 1,2-dibromobenzene. The palladium-catalyzed coupling reaction of 1,2-dibromobenzene with methoxyphenylmagnesium bromide or methoxyphenylboronic acid provided methoxy substituted 2-bromobiphenyls. Lithium–bromine exchange with n-butyllithium, followed by reaction with dimethyl carbonate afforded