$re = '/^(?:[^ \n]* ){5}\[(?P<username>\w+)(?:\].*\])(?P<IP>[^:]+)/';
$str = 'Oct 24 18:43:57 openvpn[36372]: 66.103.224.123:59349 [username] Peer Connection Initiated with [AF_INET]66.103.224.123:59349';
preg_match_all($re, $str, $matches, PREG_SET_ORDER, 0);
// Print the entire match result
var_dump($matches);
Please keep in mind that these code samples are automatically generated and are not guaranteed to work. If you find any syntax errors, feel free to submit a bug report. For a full regex reference for PHP, please visit: http://php.net/manual/en/ref.pcre.php