VSi2 is Titanium Disilicide-like structured and crystallizes in the hexagonal P6_222 space group. The structure is three-dimensional. V is bonded in a distorted q6 geometry to ten equivalent Si atoms. There are a spread of V–Si bond distances ranging from 2.51–2.67 Å. Si is bonded in a 10-coordinate geometry to five equivalent V and five equivalent Si atoms. There are a spread of Si–Si bond distances ranging from 2.48–2.67 Å.