Personally, I would back up the whole configuration folder as it ALSO has saved clips, saved searches as well as dictionaries.
By default the folder is hidden:
If Sigil still runs: Edit: Preferences: (click the button at the bottom left)
Copy all or Backup the containing (Sigil) folder
If you need to get at it the hard way
XP C:\Documents and Settings\<your_user_name>\Local Settings\Application Data\sigil-ebook\sigil
Vista and W7 C:\users\<your_user_name>\Local Settings\Application Data\sigil-ebook\sigil
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