Rob Richards kindly sent me the following response via email - posting it here as he's not subscribed.
You need to register a namespace for XPath since there's a default namesapce.
$xml = simplexml_load_file('test.xml');
/* Register arbitrary namesapce prefix for xpath*/
$xml->registerXPathNamespace('p', 'http://webservices.amazon.com/AWSECommerceService/2005-02-23');
$query = '//p:ItemLookupResponse';
$result = $xml->xpath($query);
var_dump($result);
Just to add to this: the registerXPathNamespace method is only present in CVS/snapshot builds and is scheduled for the 5.1 release.
Cheers,
Simon
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