4Ni-Al layered double hydroxide (LDH) precursors were prepared by the following three methods: constant pH coprecipitation, variable pH coprecipitation and urea hydrolysis. The 4Ni-Al mixed metal oxide (MMO) catalysts were obtained by the calcination of LDH precursors at 600 °C, and their catalytic performances in ODHP from 350 to 550 °C were tested. The 4Ni-Al MMO from the urea hydrolysis method showed a higher and more stable propylene selectivity of ca. 40% with propylene yield of ca.11% at 500 °C, and that from the constant pH coprecipitation method was followed, while oxidative cracking of propane occurred on the 4Ni-Al MMO from the variable pH coprecipitation method. It is considered to be closely related to the dispersion and stability of the surface Ni(II) species through comprehensive analysis of XRD, N 2 -adsorption-desorption, TEM, XPS, H 2 -TPR and In-situ electrical conductivity. The urea hydrolysis method with a low salt concentration, leading to an excellent stability of the surface Ni(II) species at high reaction temperature, should be selected to prepare Ni-Al MMO catalysts for ODHP instead of the traditional variable pH coprecipitation method with a high salt concentration.