High-quality and stable PS@TiO2 core-shell microsphere colloidal crystals were prepared by electrostatic colloid stabilization combined with two-substrate vertical deposition method. The polyelectrolyte stabilized colloids self-assembled into face-centered cubic arrays with the (111) face perpendicular to the substrate. These colloidal crystals are gifted with high mechanical stability toward the How of solution. Structure-property correlations were made using scanning electron microscopy and UV-vis-NIR spectroscopy. Optical spectra showed the presence of an L-stopband peak in the photonic band structure. Besides, these PS@TiO2 colloidal crystals can be used as templates to fabricate the nonspherical macroporous materials, and complete band gaps can be more easily obtained from such structure than from their spherical counterparts due to their lower symmetries. This work will hold the promise of enhanced photonic band gap materials. (C) 2008 Elsevier Inc. All rights reserved.