Although γ/η-Mo₄O₁₁ and Mo₂Ta₂O₁₁ are used in a variety of industrial applications and can easily be synthesized in a chemical vapour transport (CVT) process or reactions in silica ampoules, respectively, only few data are available concerning their physical properties. In this paper, we further explore the properties of the three compounds with respect to their thermal and magnetic behavior, surface composition, and Raman spectroscopic properties.