A series of Cr‐based metal–organic framework MIL‐101‐SO3H bearing sulfonic acid functional groups were utilized for the immobilization of catalytically active copper species via a post‐synthetic metalation method. The novel materials were fully characterized by scanning electron microscopy, X‐ray diffraction, energy dispersive X‐ray spectroscopy (EDX), X‐ray photoelectron spectroscopy (XPS), the Brunauer–Emmett–Teller method, and thermogravimetric analysis. XPS and the EDX element map both suggested that Cu2+ is coordinately bonded to the MIL‐101‐SO3H, which forms the MIL‐101‐SO3@Cu structure. The obtained copper‐doped MIL‐101‐SO3@Cu‐1, MIL‐101‐SO3@Cu‐2, and MIL‐101‐SO3@Cu‐3 catalysts were utilized in the selective oxidation of alcohols and epoxidation of olefins using molecular oxygen as an oxidant. Catalytic aerobic oxidation optimization showed that MIL‐101‐SO3@Cu‐1 is the optimal catalyst and it can be reused ten times without compromising the yield and selectivity.