I open a PNG with Preview, then drag another one into the sidebar, and then choose Export to PDF. The resulting PDF has only one page.
I tried again, after selecting all pages -- same result.
How do I export a multipage PDF?
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It saves one file to PDF. It doesn't concatenate first. For whatever reason that was decided, that's what it does.
The quick workaround is to go to Print, then save as PDF from there. This will save all pages opened in the same window.