To investigate the effect of the catalyst synthesis method on the oxidative dehydrogenation (ODH) of nbutenes, BiFe0.65MoP0.1 oxide catalysts were prepared with various synthesis methods such as co-precipitation, citric acid method, hydrothermal method, and surfactant templated method. The catalysts were characterized by X-ray Diffraction (XRD), N2 sorption, and NH3/1-butene-temperature programmed desorption (NH3/1-butene-TPD) to correlate with catalytic activity in ODH reaction. Among the catalysts studied here, BiFe0.65MoP0.1 oxide catalyst prepared with co-precipitation method marked the highest activity showing 1-butene conversion, 79.5%, butadiene selectivity, 85.1% and yield, 67.7% after reaction for 14 h. From the result of NH3-TPD, the catalytic activity is closely related to the acidity of the BiFe0.65MoP0.1-x oxide catalyst and acidity of the BiFe0.65MoP0.1 oxde catalyst prepared with co-precipitation method was higher than that of other catalysts. In addition, combined with the 1-butene TPD, the higher catalytic activity is closely related to the amount of weakly adsorbed intermediate (<200 oC) and the desorbing temperature of strongly adsorbed intermediates (>200 oC).