The biggest use I personally make of it is where I am importing books where the title and author fields are not set, such as by the book having a random filename. Rather than manually typing it in you could extract isbn and do a metadata download with the option to overwrite title and author.
Metadata downloads with an isbn will all but guarantee you a better likelihood of the right metadata from the website, since most metadata plugins will lookup by isbn if available and fallback to title and author search if not. The latter being more error prone due to spelling errors, typos, series info in title field etc.
And a small minority undoubtedly use it because they are sufficiently fussy to want the isbn field to contain the value for thei specific edition of that book.
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