Hi Dean, I've made an epub from Open Office, I'm sure Libre works the same. For a TOC highlight the chapter title, then 'bookmark' from the 'insert' menu. The whole process of TOC creation is explained in the video that has a link in the Smashwords Style Guide, available from the SW site.
Oddly enough, despite having successfully published at SW before, in my latest book I've encountered a problem with the TOC, that's truly bizarre! I'm just about to start a thread to seek help.
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