$re = '/<<(?>(?>[^\\\\>]*)(?>>(?!>))?)*+\\\\(?>(?>[^>]*)(?>>(?!>))?)++>>/';
$str = 'Account number: <<@Account.AccountNumber>>
<<@Am\\hich\\af1\\dbch\\af31505\\loch\\f1 ount>>
<<@Amount>>
<<Where: Phrase =\\ @Value>>\\<<hi>>\\hi<<hi>>
<<\\hich\\af1\\dbch\\af31505\\loch\\f1 @Amount>>
<<@Amount\\hich\\af1\\dbch\\af31505\\loch\\f1 >>
<<Where: Column > Value>>
<<Where: Column\\hich\\af1\\dbch\\af31505\\loch\\f1 > Value>>
<<Where: Column > \\hich\\af1\\dbch\\af31505\\loch\\f1 Value>>
';
preg_match_all($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