There has been increasing research interest in the study of molecular-based magnetism. A rational design of nitroxisides with magnetic cooperativity using the intermolecular magnetic coupling is described. Introducing the hydrogen bonding site into nitroxides is a useful way of controlling magnetic interaction and/or molecular arrangement in crystal. Nitronyl nitroxide with imidazole (Im-NN) and benzimidazole (BIm-NN) were designed and their self-assembled structures and magnetic properties were characterized according to McConnell's theorem. BIm-NN were assembled in a columnar structure with N-H…O-N motif and formed a 1-D ferromagnetic chain due to the overlap of magnetic orbitals. The effect of hydrogen bonding on the molecular packing was also observed with nitronyl nitroxides having hydrophobic chain. Spectroscopic property of nitronyl nitroxides at air-water interface was discussed in terms of their electronic structure.