Polystyrene (PS) colloidal crystal multilayers with high crystalline quality are fabricated quickly from aqueous colloidal solutions by the vertical deposition method at certain temperature and humidity. Optical properties, which are determined by the photonic band structure, are discussed by means of light transmission and reflection measurements. By scanning electron microscopy (SEM), the morphology of the samples is characterized and the ordered close package of the spherical colloids in planes parallel to the substrate surface is illustrated. Furthermore, facecenteredcubic (fcc) phase is proved by transmission ele ctron microscope (TEM). To avoid friability and redispersal, the colloidal c rystals multilayers are dried slowed and sintered at 105℃ for 6 hours to enlarg ement of the contact section between nearestneighbor PS spheres. Experiments h ave proved the efficiency and practicability of the method.