Morphology of vanadium slags were investigated by scanning electron microscopy (SEM). The mineralogical phases were characterized by energy disperse X-ray spectrometry (EDS) and powder X-ray diffraction (XRD). The obtained results show that spinels and silicates are the major phases in the vanadium slag, and V is concentrated in Fe x V 3-x O 4 and Mg x (V, Ti) 3-x O 4 . Both the spinel grain size and volume fraction in the slag with higher V 2 O 3 content are much larger than that with lower V 2 O 3 content. (Fe, Mn) 2 SiO 4 and (Fe, Mn)SiO 3 have a higher proportion in the slag with lower V 2 O 3 and higher SiO 2 content. The relation among cooling conditions and grain size and volume fraction of spinels is also discussed. It is found that low cooling rate and long holding time benefit spinel crystal growth, especially for the interval of 1200-1250 °C. Both mean diameter and volume fraction of spinels could achieve or exceed the industry vanadium slag when holding more than 45 min.