During the layer-by-layer (LbL.) electrostatic assembly process, we orient organic molecules (nickel phthalocyanine) by an external magnetic field. Orientation of the magnetic moment of the molecules in a monolayer is immobilized by depositing a monolayer of a suitable polycation. Due to the orientation of magnetic moments, the electrostatic adsorption process becomes enhanced in subsequent layers. By cycling the deposition sequence layer after layer. we have achieved highly ordered and closely packed LbL. films of the molecules with their magnetic moments oriented perpendicular to the substrate. Nonmagnetic copper phthalocyanine expectedly showed neither a magnetic-field assisted alignment nor an enhanced adsorption in LbL film deposition process.