After upgrading to libreoffice-4.1.0.4-6.fc19 I have problems opening some xls files, I get "General I/O error". I think the problem is for files with xls extension but that don't have regular xls content. For example trying to open an html table like http://www.danieletabacco.com/esempi/genera_excel.php gives the error. If I downgrade to libreoffice-calc-4.1.0.0-9.beta2.fc19 the import dialog is showed and the file opens. Not sure if libreoffice-4.1.1.1-1.fc20 resolve the bug, if you can build a version for F19 I will try it.
Let me see if I find anything.