A series of bismuth molybdate catalysts with relatively high surface area was prepared via mild hydrothermal synthesis. Variation of the pH value and Bi/Mo ratio during the synthesis allowed tuning of the crystalline Bi-Mo oxide phases, as determined by X-ray diffraction (XRD) and Raman spectroscopy. The pH value during synthesis had a strong influence on the catalytic performance. Synthesis using a Bi/Mo ratio of 1/1 at pH ≥ 6 resulted in γ-Bi2MoO6, which exhibited a better catalytic performance than phase mixtures obtained at lower pH values. However, a significantly lower catalytic activity was observed at pH = 9 due to the low specific surface area. γ-Bi2MoO6synthesized with Bi/Mo = 1/1 at pH = 6 and 7 exhibited relatively high surface areas and the best catalytic performance. All samples prepared with Bi/Mo = 1/1, except samples synthesized at pH = 1 and 9, showed better catalytic performance than samples synthesized with Bi/Mo = 2/3 at pH = 4 and 9 and γ-Bi2MoO6 synthesized by co-precipitation at pH = 7. At temperatures above 440 °C, the catalytic activity of the hydrothermally synthesized bismuth molybdates started to decrease due to sintering and loss of surface area. These results support that a combination of the required bismuth molybdate phase and a high specific surface area is crucial for a good performance in the selective oxidation of propylene.