" Tools > Options > LibreOffice > Paths" does not have a way to change the default “Export as PDF” Location.
No, but if you double-click on any of the paths shown, such as the path to My Documents (which is the default destination for saving documents in my version of LO), then you can navigate to whichever destination you want. Just remember to reset it to the default after you have exported your particular document.
The “Export as PDF” function uses as default folder the one associated to “My Documents” in the configuration (Tools > Options > LibreOffice > Paths ).
It works this way in my version 7.0.3
That’s shame. I like exporting it to the folder in which the originating file resides, which is the way it works in 6.4.7 and earlier. Al 
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