First of all, it would be interesting to know the actual content of the file.
Calc can not open html directly but there are all kinds of files out there
which share the .xls suffix in order to trigger the Excel application. Calc
does not care about the file name suffix. If the file has a well known
"taste" it will be opened regardless of the name suffix.
Just open your file in a text editor (notepad). Or open it in a browser and
view the source code. Most likely it is a plain text file.

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