AbstractWe here report the development of new thermotropic colloidal liquid‐crystalline (LC) organic/inorganic hybrids consisting of a hydroxyapatite (HAp)/poly(acrylic acid) (PAA) nanorod and a dendritic forklike mesogen. Complexation of the HAp/PAA nanorod covered with negatively charged PAA and a cationic forklike mesogen through electrostatic interactions and cation metathesis results in the surface modification of the HAp/PAA nanorod with the forklike mesogen. While the HAp/PAA nanorod forms a lyotropic colloidal LC phase in the aqueous dispersion, the HAp/PAA nanorod modified with the forklike mesogen exhibits thermotropic colloidal LC phases in the solvent‐free states. The biomineral‐based organic/inorganic colloidal liquid crystals exhibiting thermotropic LC properties have potential for the development of new stimuli‐responsive sustainable materials.