Pos yasta aquí están los codes 
Cambiar imagen al pasar el Mouse en VB.NET (Google indexando)
Private Sub picMini_MouseEnter(sender As Object, e As EventArgs) Handles picMini.MouseEnter
sender.Image = Mini_Off
End Sub
Private Sub picMini_MouseLeave(sender As Object, e As EventArgs) Handles picMini.MouseLeave
sender.Image = Mini_On
End Sub
Private Sub frmMain_Load(sender As Object, e As EventArgs) Handles MyBase.Load
picMini.Image = Mini_On 'Aqui se carga la que se va a mostrar por defecto
picMini.BackColor = Color.Transparent 'Por si tiene transparencias la imagen
Dim Mini_Off As Image = Image.FromFile(".\Art\Buttons\Mini_Off.png")
Dim Mini_On As Image = Image.FromFile(".\Art\Buttons\Mini_On.png")
(Para los que seáis unos negros y no sepáis las propiedades un Form como yo
)
Dim Fondo As Image = Image.FromFile(".\Art\fondo.jpg")
Dim ancho As String = Me.Width
Dim alto As String = Me.Height
Dim bm_source As Bitmap = New Bitmap(Fondo)
Dim bm_dest As New Bitmap(CInt(ancho), CInt(alto))
Dim gr_dest As Graphics = Graphics.FromImage(bm_dest)
gr_dest.DrawImage(bm_source, 0, 0, bm_dest.Width + 1, bm_dest.Height + 1)
Me.BackgroundImage = bm_dest
Un saludo. 
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