A new category of hydroxide ion exchange membrane bearing ordered interpenetrating network (semi-IPN) structure established by electric field poling during membrane formation, lead to balanced property where high ion conductivity and low alcohol (methanol and ethanol) permeability co-existed. Success of this membrane preparation scheme is illustrated with the semi-IPN membrane formed by dendritic modified bismaleimide (mBMI) and polyvinyl alcohol (PVA) hydrogel casted together under applied electric field (E-field> 2000V/cm, Ac=1-20Hz,). Detailed morphology and water diffusion studies shows electric field poling establishes higher ordered amorphous domains that induces preferentially oriented conducting path that raised ion conductivity. On the other hand, semi-IPN network effectively reduces methanol and ethanol permeation and improves membrane toughness. When PVA:mBMI equals 2 to 3 weight ratio, the membrane delivered impressive room temperature OH ion conductivity of 38.2 mS/cm and a substantially reduced ethanol permeation of 7.7x10^-8 cm²/s; giving exceedingly high ethanol selectivity ratio (~10⁶) with electric field poling preparation. Ordering in the semi-IPN structure by electric field poling also causses densification of the amorphous domain that leads to improved chemical stability (99wt% mass retention in 6M KOH for nearly a month) and mechanical toughness (Tensile strength increased from 3.5 MPa to 7.0 MPa, and elongation at break raised from 60% to 92%). The study concludes the application of an external electric field initiated reorganization of membrane morphology where high performance fuel cell membrane bearing high ion conductivity; low fuel permeation; high membrane strength; and high chemical stability can be established, simultaneously.