The assembly of aniline molecules was controlled using single-crystalline ice facets that have highly ordered but dissimilarly organized OH groups at the surface. We found a difference in electrical properties of polyaniline nanofilms synthesized on dissimilar ice surfaces; basal, primary prism, and secondary prism planes. We discovered through molecular dynamics that ice-directed self-assembly induced layered structures of aniline monomers depending on enhanced formation of hydrogen bonding network per ice facet. The anilines assembled better-ordered on secondary prism plane and their lattice coincided with a repeat distance of H2O molecules on ice. This resulted in improved electrical properties of polyaniline nanofilms after subsequent polymerization.