The systems Nb 2 O 5 -Ta 2 O 5 and Nb 2 O 5 -V 2 O 5 were investigated using thermal analysis, X-ray powder diffraction and thermodynamic simulations. Solid solution formation is possible for both systems; furthermore, both contain one intermediate compound, VNb 9 O 25 or Ta 2 Nb 4 O 15 , respectively. Phase relationships for pure niobium(V)-oxide and tantalum(V)-oxide were studied under ambient pressure. It was found that both compounds can occur in two stable solid modifications. For niobium(V)-oxide this are the monoclinic high-temperature modification (H-Nb 2 O 5 ) and an orthorhombic low-temperature modification (T-Nb 2 O 5 ) and for tantalum(V)-oxide a tetragonal high-temperature form (α-Ta 2 O 5 ) and an orthorhombic low-temperature form (β-Ta 2 O 5 ). Based on these results, crystal growth experiments with various compositions from both systems were carried out using the optical floating zone (OZF) technique.