Our initial studies were carried out with the commercially available 4-biphenylol 1a and SO2F2 2a. Pleasingly, in the presence of 10 mol% triethylamine and 800 mg molecular sieves 4Å, the reaction proceeded smoothly in acetonitrile at room temperature to form aryl fluorosulfate 3a in 94% yield (Table , entry 1). Encouraged by this result, other common bases were then examined. The Hünig's base catalyzed the reaction in 95% yield (Table , entry 2). DMAP, DABCO and cinchonine catalyzed the reaction in good yields (Table ). Organic superbases DBU, DBN, TBD and TMG catalyzed the reaction in high yields ( With the optimized reaction conditions in hand, we then examined the scope of phenols and the results are summarized in Table . Both electron-donating and electron-withdrawing substituents substituted phenols participated in the SuFEx reaction well, producing the corresponding aryl fluorosulfates in high yields. The electronic properties and different positions of the substituents have little influence on the rection yield (3b-3t). Many useful groups, such as halogenations (3e-3g, 3m-3o), nitrile (3h), aldehyde (3l), ketone and ester group (3i and 3j) were tolerated well.