Reliable procedures for the controlled synthesis of phase-pure MoVTeNb mixed oxides with M1 structure (ICSD 55097) and tunable crystal dimensions were developed to study the structure sensitivity of the selective oxidation of propane to acrylic acid. A series of powdered M1 catalysts was successfully prepared on a gram scale by using a hydrothermal-based route, purification of biphasic M1-M2 (M2 phase – ICSD 55098) oxide systems, and an innovative approach utilizing a superheated water vapor treatment of calcined precursors. The influence of the preparation technique on the particle morphology and the size is discussed. Detailed experimental studies highlight that the as-derived catalytic materials were indeed phase-pure and compositionally uniform MoVTeNb oxide M1 powders, composed of single-crystalline and structural defect-free crystals grown along the c axis. The morphologically different catalysts were studied in the selective oxidation of propane to acrylic acid, revealing that active sites appear on the entire M1 surface and illustrating the high sensitivity of catalyst performance on the catalyst synthesis method.