This is probably what you want:
use XML::LibXML;
use XML::LibXML::XPathContext;
{
my $xml = <<'XML';
<?xml version="1.0" standalone="yes"?>
<sdnList xmlns="http://tempuri.org/sdnList.xsd">
<sdnEntry>
<lastName>Hello world!</lastName>
</sdnEntry>
</sdnList>
XML
my $parser = XML::LibXML->new;
my $doc = $parser->parse_string($xml);
my $xc = XML::LibXML::XPathContext->new($doc);
$xc->registerNs('sdnList', 'http://tempuri.org/sdnList.xsd');
my $result = $xc->findvalue('//sdnList:lastName');
is( $result, "Hello world!", "Namespace" );
}