Membrane technology could serve as an energy-efficient alternative for thermal fractionation of hydrocarbon mixtures, yet membrane separation of hydrocarbon mixtures puts forward strict requirements for membrane materials to tolerate the hydrocarbon infiltration with simultaneously precise molecular differentiation. Polyimides are universal engineering plastics with a wide range of applications including commercial membrane fabrication, but existing polyimide membranes could not accomplish hydrocarbon separation with viable efficiency. Polyimides with contorted molecular chain segments and abundant interconnected micropores could realize fast permeation of target molecules, yet microporous polyimides are prone to swelling in organic solvents. The strategy of chemical cross-linking has been well used for organic solvent resistant membranes, but chemical cross-linking reactions interfere the original polymer backbone structure and significantly affects the membrane permeability and mechanical properties. This talk demonstrates the feasibility of metal ion cross-linking as a membrane stabilizing strategy in organic solvent environments. Carboxyl functional groups are introduced into a microporous polyimide backbone for metal ion coordination cross-linking to reaction takes place. Especially, the Cu²⁺ ion cross-linked polyimide membranes exhibit good stability in a variety of organic solvents without significant attenuation of membrane permeability. Moreover, this talk also covers our recent effort on the design of a series of fluorinated microporous polyimides with metal ion crosslinked hydrophobic contorted structure for liquid hydrocarbon separation. The polyimides-based membrane exhibits toluene permeability up to 0.29 L m^-2h^-1bar^-1 and >80% rejection to hydrocarbons with molecular weights greater than 170 Da. Through a two-stage membrane cascade process, an efficient enrichment of gasoline content to 96.8% from a 1:1 gasoline/diesel mixture, and a more exciting separation of a real light crude oil feed is achieved by the polyimide membrane. This talk presents an effective approach for designing membranes made of engineering polymers towards practical organic solvent and crude oil separation applications.