I rely heavily on LibreOffice and am hesitant to upgrade unless I can be as sure as possible that LibreOffice (Writer) will run.
Can anybody confirm that the software works and does not crash on Mavericks?
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You can choose to override your security settings and open the app anyway.
The app is saved as an exception to your security settings, and you will be able to open it in the future by double-clicking it, just like any authorized app.