Tailoring the interface between the polymer matrix and filler to probe the structure-performance relationship is one of the critical research issues in hybrid membranes. In this study, metal organic framework (MOF) incorporated hybrid membranes are fabricated with polydimethylsiloxane (PDMS) as the matrix and Cu(II) loaded UiO-67-bpydc (bpydc refers to 2,2'-bipyridine-5,5'-dicarboxylic acid) as the filler, which are utilized for removing thiophene from model gasoline. The structure-performance relationship of the resultant membranes was investigated. The flux of the hybrid membrane shows a remarkable increase while avoiding obvious loss of selectivity. The loading of Cu(II) onto UiO-67-bpydc effectively tailors the interface between the polymer matrix and filler, which enhances the membrane separation performance. This study may offer a new example for designing MOF-based hybrid membranes towards efficient molecular separation.