Formation of phenonium ions through anchimeric assistance (neighboring-group participation) of aryl rings has been known since 1949. Although these reactive intermediates have been studied extensively by physical organic chemists, their potential as control elements in synthesis is underutilized. Presented here are our laboratory’s recently reported first examples of regiodivergent openings of nonsymmetrical phenonium ions with chloride nucleophiles. The selectivity of these processes is under reagent control. The reactions are operationally simple and permit the stereospecific synthesis of complex chiral building blocks from readily accessible epoxide starting materials.1 Introduction2 Select Examples of Phenonium Ion Methodology3 Regiodivergent Opening of Nonsymmetrical Phenonium Ions4 Summary and Outlook