I\'ve got a DropDownList and I\'m trying to prevent it from being used as an attack vector. Can I assume that the user is unable to actually change the values of the DDL and
Actually you should be able to assume that the dropdown list options have not been changed client side as long as the page has EnableEventValidation = true (which is default although you can disable it per page or in the web.config). If a new value is added to your dropdownlist client side, and a postback occurs an error will occur unless you register this new value for event validation (http://odetocode.com/blogs/scott/archive/2006/03/21/asp-net-event-validation-and-invalid-callback-or-postback-argument-again.aspx)
No, you can't assume that.
You should always consider that all input is untrusted, and treat it appropriately (make sure it is what it should be, and that it is of the right type, and that the current user (or whatever) has access to it, and so on).