You can use
XML::LibXML::XPathContext to register the namespace as follows:
use strict;
use warnings;
use XML::LibXML;
use XML::LibXML::XPathContext;
# load the XML doc
my $p = XML::LibXML->new;
my $xml_file = do { local $/; <DATA> };
my $dom = $p->parse_string( $xml_file );
# register the namespace
my $xc = XML::LibXML::XPathContext->new( $dom );
$xc->registerNs('ns', 'http://www.w3.org/2005/Atom');
# select using XPath
my @nodes = $xc->findnodes( '/ns:feed/ns:entry');
print $_->toString for @nodes;
__DATA__
<?xml version="1.0" encoding="UTF-8"?>
<feed xmlns="http://www.w3.org/2005/Atom" xmlns:os="http://a9.com/-/sp
+ec/opensearch/1.1/">
<os:totalResults>233</os:totalResults>
<os:startIndex>1</os:startIndex>
<os:itemsPerPage>233</os:itemsPerPage>
<os:Query role="request" searchTerms="test" startPage=""/>
<entry>
<id>34</id>
<channel>1</channel>
<title>Decision making: Marmite</title>
+ <description>A meeting of the 'business group', which is the committ
+ee set up to steer the development of the new Squeezy Marmite bottle.
+ They discuss the qualities of the new bottle and agree to test i
t with consumers.</description>
<author></author>
<size>36145156</size>
<date>2007-09-07</date>
<uri>assets/asset10000/aaiiaaaaaaafnknn.mpg</uri>
<keylearningstage></keylearningstage>
<keywords></keywords>
<source>C4L Secondary Service</source>
</entry>
</feed>