Ni(II)/Ti(IV) layered double hydroxide (LDH) was synthesized by homogeneous precipitation method utilizing urea hydrolysis. The structure and composition of the LDHs were characterized by PXRD, FT-IR, ICP-AES, SEM, nitrogen adsorption/desorption isotherms, TG-DTA, and in situ high temperature X-ray diffraction techniques. It was found that Ti 4+ cation are incorporated in the host layers with cyanate anion as the interlayer anions. The titanium content incorporated in the LDH slabs increases with prolonged synthesis time. The Ni–Ti-LDH crystallinity decreases with increasing Ti 4+ dosage in the synthesis mixture. No extra-framework titanium species was observed existing in the Ni–Ti-LDH. Both the surface area (182 m 2/g) and pore volume (0.86 cm 3/g) for the LDH synthesized using the urea method are higher than that by conventional methods. The Ni–Ti-LDH is converted to Ni–Ti-LDO above 473 K.