WordPress mysqli and PDO

WordPress uses mysql_* functions.

http://core.trac.wordpress.org/browser/tags/3.5.1/wp-includes/wp-db.php

It has used those ever since I can remember, which probably answers your last question. It is what I would consider legacy code. I suspect it will be updated sometime soon (those functions were only deprecated as of PHP 5.5, I believe). I don’t know which route development will go.

Link to a ticket in Trac, courtesy of Wyck (from a comment below):

http://core.trac.wordpress.org/ticket/21663

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