Site‐selective direct acetoxylation of pyrazolones was accomplished by utilizing an easy‐to‐handle (diacetoxyiodo)benzene (PIDA) as the sole acetoxylating reagent. In the presence of Pd(OAc)2 catalyst, the 4‐acetoxylated pyrazolone product was exclusively formed. Meanwhile, in the absence of Pd(OAc)2, the pyrazolone methyl acetate product was obtained over the Csp2–H bond functionalization. Both switchable approaches have been successfully applied to various pyrazolone substrates, giving the corresponding products in moderate to high yields under mild conditions.