Nearly monodisperse nanoparticles have been synthesized based on a naturally occurring polymer of hydropropylcellulose (HPC) using precipitation polymerization method. It is found that when the polydispersity index value of the HPC nanoparticles is less than 1.10, the HPC particles can self-assemble into an ordered structure, displaying bright colors. UV-visible spectroscopy reveals that the color shifts to a lower wavelength as the interparticle distance decreases following the Bragg diffraction equation. The HPC nanoparticle assembly in water has been further stabilized by covalently bonding neighboring particles to form a three-dimensional network. This network contains a large amount of water similar to a conventional bulk gel but displays colors as a result of its ordered structure.