Does it launch correctly if you double click the launcher icon on the desktop (before you've dragged it to Cairo)?
If you right click on the desktop icon and then select properties, what is listed in the "Command" field?
Also, can I just confirm that you are talking about the general Libre Office link (similar to
https://upload.wikimedia.org/wikiped...n_Icon.svg.png), not the Libre Office Word link?
Finally, because we're talking potentially about desktop-related stuff, which desktop environment are you using?