High-resolution transmission electron microscopy characterization of molybdenum oxide catalyst precursors is carried out for a better understanding of the mechanisms leading to the active catalytic material. The precipitated material consists of both large-unit cell crystals and randomly orientated clusters on a 3-5 nm scale. The crystalline clusters are embedded in non-crystalline material, preventing the formation of large well-defined inactive orthorhombic MoO(3) crystals during activation of the catalyst material.