We report here that a two-dimensional (2D) diamond-like structure of micron-sized colloidal particles can be obtained by layer-by-layer self-assembly. Positively and negatively charged silica particles, 1 μm in diameter, were used in the experiments. On a positively charged, flat glass substrate, the first layer of negatively charged particles was prepared to form a non-close-packed 2D crystal. Then the second and third layers were fabricated using electrostatic adsorption. The positions of adsorbed particles were controllable by tuning the zeta-potential of the particles and the salt concentration of the medium. The FDTD calculations show that the 2D diamond structures of particles with higher refractive index (titania) have an absorption band in the wavelength range corresponding to the photonic band gap of the 3D bulk crystal. We expect these findings to be useful for the fabrication of novel photonic materials.