Saw this on another answers page. You can't modify a WWWForm's headers directly, you have to create your own:
(C#)
var form = new WWWForm();
form.AddField( "SomeKey", "SomeValue" );
var headers = new Hashtable();
headers["SomeHeaderKey"] = "SomeHeaderValue";
var www = new WWW( url, form.data, headers );
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