The Suzuki coupling reactions of (4‐X‐Ph)Ph2P˭O, where X = bromide or triflate, with a series of boronic acids were studied using tetrakis‐(triphenylphosphino) palladium or palladium acetate as the catalyst. The boronic acids utilized were phenyl, p‐tolyl, 3‐methoxy, 4‐methoxy, and 4‐acetyl. Yields of the corresponding biphenyl analogues ranged from 50 to 95%. Palladium acetate provided products free of triphenylphosphine contamination, and required significantly shorter reaction times for complete reaction (2 to 4 hours vs. 12 to 24 hours, respectively) than when tetrakis‐(triphenylphosphino) palladium was used. The methodology was applied to bis(4‐F‐Ph)(4‐OTf‐Ph)P˭O to afford, in excellent yield (99%), a biphenyl‐based AB2 monomer precursor for dendritic and hyperbranched poly(arylene ether phosphine oxide)s.