Most of the WordPress PDF plugins out there use services like Joliprint and Print Friendly to convert posts to PDFs.
Is there a plugin that does this locally utilizing the power of PHP (and/or WordPress), I mean, without using an external service?
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I was half way through writing a long answer explaining why there weren't any ... when I found one.
WP Post to PDF is a plugin, updated for WP 3.3.2, that generates PDFs locally and caches them for later.