Will Debian 10 official "just work" on Librem 14?

It should. You might have some disatvantages, like not being able to make use of the work Purism puts in the free EC, and probably you don’t have many advantages over PureOS, which is 99% Debian plus some Purism sugar sprinkled on top.

If you want the additional packages, I think it should be safe to add the Debian contrib / non-free repos (but not Debian main)

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