I'm seeing the same issue here too.
For me, I noticed it when editing a custom metadata field (Text, but with a fixed set of permitted values) in the Metadata Editor.
If I click the dropdown and choose the top "null" field, there's no error. However, if I choose the recycle button to "nullify" the field, I get the error, so the bug seems to live somewhere in there.
I've never seen this issue in a situation like this (a field with all valid values) in the many years I've used Calibre.
NOTE:
I have seen this (I think like @ownedbycats) when I'm doing bulk metadata shuffling and have deleted an entry in a field before resetting/removing it in the records. I'm assuming most ppl here know what I'm talking about, but I can explain this in more detail if needed.
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