I wanted to ask & answer this here for the benefit of others. The reverse question was answered at How do I change default paper settings from "letter" to "A4"? - #17 by JohnCyrmu, and the answer for this is very similar.
If your paper size is A4 and your locale setting in LibreOffice is “Default - English (USA)” then choosing “English USA” (no “Default -”) will fix it, which is to say that it will make the paper size default to Letter, not A4.
To make the change, go to Tools → Options… → Language Settings → Languages, and then choose the value from the Formats → “Locale setting” dropdown.