It's configured at build time. You can see how your PHP installation was configured by looking at the Configure Command in the output from phpinfo();
For more information on PHP configure options see PHP Installation and Configuration. Also php-build — Builds multiple versions of PHP might be of help or interest.
Note for Ubuntu users
You won't find the configure command in the phpinfo output, see this bug marked as invalid. Here are some links to code mentioned in the bug report.
Example Configure Command from phpinfo():
Configure Command => './configure' '--build=i686-redhat-linux-gnu' '--host=i686-redhat-linux-gnu' '--target=i386-redhat-linux-gnu' '--program-prefix=' '--prefix=/usr' '--exec-prefix=/usr' '--bindir=/usr/bin' '--sbindir=/usr/sbin' '--sysconfdir=/etc' '--datadir=/usr/share' '--includedir=/usr/include' '--libdir=/usr/lib' '--libexecdir=/usr/libexec' '--localstatedir=/var' '--sharedstatedir=/usr/com' '--mandir=/usr/share/man' '--infodir=/usr/share/info' '--cache-file=../config.cache' '--with-libdir=lib' '--with-config-file-path=/etc' '--with-config-file-scan-dir=/etc/php.d' '--disable-debug' '--with-pic' '--disable-rpath' '--without-pear' '--with-bz2' '--with-curl' '--with-exec-dir=/usr/bin' '--with-freetype-dir=/usr' '--with-png-dir=/usr' '--enable-gd-native-ttf' '--without-gdbm' '--with-gettext' '--with-gmp' '--with-iconv' '--with-jpeg-dir=/usr' '--with-openssl' '--with-png' '--with-pspell' '--with-expat-dir=/usr' '--with-pcre-regex=/usr' '--with-zlib' '--with-layout=GNU' '--enable-exif' '--enable-ftp' '--enable-magic-quotes' '--enable-sockets' '--enable-sysvsem' '--enable-sysvshm' '--enable-sysvmsg' '--enable-track-vars' '--enable-trans-sid' '--enable-yp' '--enable-wddx' '--with-kerberos' '--enable-ucd-snmp-hack' '--with-unixODBC=shared,/usr' '--enable-memory-limit' '--enable-shmop' '--enable-calendar' '--enable-dbx' '--enable-dio' '--with-mime-magic=/usr/share/file/magic.mime' '--without-sqlite' '--with-libxml-dir=/usr' '--with-xml' '--with-system-tzdata' '--enable-force-cgi-redirect' '--enable-pcntl' '--with-imap=shared' '--with-imap-ssl' '--enable-mbstring=shared' '--enable-mbstr-enc-trans' '--enable-mbregex' '--with-ncurses=shared' '--with-gd=shared' '--enable-bcmath=shared' '--enable-dba=shared' '--with-db4=/usr' '--with-xmlrpc=shared' '--with-ldap=shared' '--with-ldap-sasl' '--with-mysql=shared,/usr' '--with-mysqli=shared,/usr/lib/mysql/mysql_config' '--enable-dom=shared' '--with-dom-xslt=/usr' '--with-dom-exslt=/usr' '--with-pgsql=shared' '--with-snmp=shared,/usr' '--enable-soap=shared' '--with-xsl=shared,/usr' '--enable-xmlreader=shared' '--enable-xmlwriter=shared' '--enable-fastcgi' '--enable-pdo=shared' '--with-pdo-odbc=shared,unixODBC,/usr' '--with-pdo-mysql=shared,/usr/lib/mysql/mysql_config' '--with-pdo-pgsql=shared,/usr' '--with-pdo-sqlite=shared,/usr' '--enable-dbase=shared'