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The stoichiometric ratio for the synthesis components of hydrophobic new surface modifying macromolecules (nSMM) was altered systematically to produce three different types of nSMMs, which are called hereafter nSMM1, nSMM2, and nSMM3. The newly synthesized SMMs were characterized for fluorine content, average molecular weight, and glass transition temperature. The results showed that fluorine content decreased with increasing the ratio of α,ω‐aminopropyl poly(dimethyl siloxane) to 4,4′‐methylene bis(phenyl isocyanate). The synthesized nSMMs were blended into hydrophilic polyetherimide (PEI) host polymer to form porous hydrophobic/hydrophilic composite membranes by the phase inversion method. The prepared membranes were characterized by the contact angle measurement, X‐ray photoelectron spectroscopy, gas permeation test, measurement of liquid entry pressure of water, and …