Al-based Al-V master alloys were prepared by both the stepwise heating melting experiment and stepwise melting cooling experiment with rapid solidification to investigate the transformation of V-containing phases which gave different effects on microstructures and properties of commercial Al alloys and Ti alloys, as both melting and solidification processes affect the evolution of V-containing phases largely. The results showed that the raw Al-50wt.%V alloy consisted of needle-like Al₃V phase and Al₈V₅ phase (matrix), while petal-like Al₃V, needle-like Al₇V and plate-like Al₁₀V phase were present in the Al-V master alloys. The metastable Al₇V phase was evolved from Al₃V phase and then evolved into Al₁₀V phase during melting process. The number of Al₁₀V phase increased with the decrease of temperature in the range of 800-1000 °C. Petal-like Al₃V phases could be transformed from Al₈V₅ phase, pre-precipitated from Al-V molten liquid during melting process and precipitated directly during rapid solidification, respectively.