AbstractThe surfaces of nanodiamond particles are modified using natural castor oil‐derived 12‐hydroxystearic acid, which has thixotropic solvent properties. 12‐Hydroxystearyl chain‐modified nanodiamonds (12OHSt‐ND) are spread from a dispersion medium onto ultrapure water to afford Langmuir monolayers (a single‐particle layer) of 12OHSt‐ND exhibited a two‐dimensional phase transition from an expanded phase to a condensed phase. The surface morphology of the single‐particle layer shows a dispersed form of aggregated particles, while the layered regularity of the multilayers shows high periodicity. The surface hydrophobicity of the single‐particle layer of 12OHSt‐ND is more pronounced than that of the single‐particle layer of stearic acid‐modified nanodiamonds. The origin of the surface hydrophobicity of the single‐particle layer of 12OHSt‐ND is predicted to be the vertical conformation of the modified chains achieved via hydrogen bonding between the modified chains. In addition, the stepwise multilayers of 12OHSt‐ND exhibit various structural colors depending on the number of layers.