Pervaporation　membranes　are　potentially　useful　in　the　separation　of　aromatic/aliphatic　mixtures.　Wherein,　the　membrane　material　plays　a　key　role.　Herein,　a　series　of　functionalized　metal-organic　polyhedra　(MOPs)/hyperbranched　polymer　hybrid　membranes　are　molecularly　designed　and　fabricated　for　the　recovery　of　aromatic　hydrocarbons.　The　isostructural　MOP　molecules　with　different　functional　groups　are　uniform　in　shape/size　and　soluble　in　solvents,　which　enable　them　to　disperse　well　and　be　compatible　in/with　the　polymer.　Pervaporation　results　demonstrated　significant　improvements　of　these　membranes　in　separation　performances.　Particularly,　the　membrane　with　MOP-SO3NanHm　showed　the　separation　factor　of　8.03　and　the　permeation　flux　of　528　g/m(2)h　for　the　recovery　of　toluene　from　its　50　wt　%　n-heptane　mixture,　and　those　values　are　8.4　and　540　g/m(2)h　for　benzene/cyclohexane　mixture.　We　propose　that　the　selectivity　of　these　membranes　is　affected　primarily　by　the　polarity　of　functional　groups　in　MOPs,　which　were　further　explained　by　the　adsorption　experiments　and　molecular　simulations.　(C)　2016　American　Institute　of　Chemical　Engineers　AIChE　J,　62:　3706-3716,　2016