We investigated the liquid crystal (LC) alignment effect of the polymerized interface in the phase-separated composite film (PSCOF). Since the polymer morphology after phase separation depends highly on the LC ordering during phase separation, the azimuthal anchoring strength of the LC/polymer interface increased with highly ordered LCs. Using anchoring capability induced by imprinting effect of molecular ordering, we demonstrated a twisted nematic structure in PSCOF by application of in-plane electric fields during phase separation.