Freeze-dried sulfate intercalated layered double hydroxides (LDHs) phase was synthesized by coprecipitation method via direct intercalation of sulfate anion. The effect of freeze drying step on morphological and structural properties was investigated. The resulting phase was evaluated for its efficiency in the intercalation of the reactive azo dye, Remazol Brilliant Red 3FB (RR-3FB). As a result, the freeze-dried LDHs exhibited low crystallinity, narrow particle size distribution, highly aggregated nanoparticles and multiple-porous surface. The arrangement of intercalated sulfate was influenced by drying process resulting in a characteristic distance d003 of 8.1 Å. The intercalation of dye species was confirmed by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) analyses. The preferential arrangement of the intercalated dye species was examined, and the results show that RR-3FB molecules are partially accommodated between the LDHs layers as single-layer with horizontal orientation. The mechanism of deintercalation of RR-3FB was also examined.