Use the first: the second is confusing to read as it implies that it should read as two assignments:
role = "Administrator"
MultiLevelMenu.Visible = role
(This is one of the reasons C# is a better language than VB: the assignment operator "=" is not the same as the equality test operator "==")
If you feel you must write the second form, then at least use brackets to make it clearer:
MultiLevelMenu.Visible = (role = "Administrator")
But just because you can do something, doesn't mean you should...