Undoubtedly, there is a cleaner xpath way to do this, but I think this should help. This assumes that every url is unique (otherwise, you'll be clobbering urls).

use strict;
use warnings;
use XML::Twig;
use Data::Dumper;

my $xmlStr = <<XML;
<?xml version="1.0" encoding="UTF-8"?>

<authenticationReports>
  <generatedTime>Tue Sep 29 07:07:34 PDT 2009</generatedTime>
  <appDeploymentFile name="app-deployment.properties.hklcp.trading">
    <application name="hk">
      <urlInfo>
        <url>a/b/hk/accts_subscription</url>
        <otherPrereq>HKPwdPreReq</otherPrereq>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/accts_forms</url>
        <otherPrereq>HKPwdPreReq</otherPrereq>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/custtradingpage</url>
        <otherPrereq>BasicPrereq</otherPrereq>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/accts_userinfo</url>
        <otherPrereq>HKPwdPreReq</otherPrereq>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/headermain</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/custservicepage</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/accts_transfermoney</url>
        <otherPrereq>HKPwdPreReq</otherPrereq>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/userprereq</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/indices_us</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/homeloggedmessage</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/lead</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/orderviewmin</url>
      </urlInfo>
      <urlInfo>
        <url>a/b/hk/accts_changelogin</url>
        <otherPrereq>SessionPreReq</otherPrereq>
      </urlInfo>
    </application>
   </appDeploymentFile>
</authenticationReports>
XML

my %urls;
my $twig= new XML::Twig(
    twig_handlers => { 'appDeploymentFile' => \&appdep }
);
$twig->parse($xmlStr);
print Dumper(\%urls);
exit;


sub appdep {
    my ($t, $adep) = @_;
    my $name = $adep->att('name');
    for my $urli ($adep->first_child('application')->children('urlInfo
+')) {
        $urls{ $urli->first_child('url')->text() } = $name;
    }
}

__END__
$VAR1 = {
          'a/b/hk/accts_subscription' => 'app-deployment.properties.hk
+lcp.trading',
          'a/b/hk/accts_changelogin' => 'app-deployment.properties.hkl
+cp.trading',
          'a/b/hk/lead' => 'app-deployment.properties.hklcp.trading',
          'a/b/hk/orderviewmin' => 'app-deployment.properties.hklcp.tr
+ading',
          'a/b/hk/headermain' => 'app-deployment.properties.hklcp.trad
+ing',
          'a/b/hk/custservicepage' => 'app-deployment.properties.hklcp
+.trading',
          'a/b/hk/custtradingpage' => 'app-deployment.properties.hklcp
+.trading',
          'a/b/hk/accts_userinfo' => 'app-deployment.properties.hklcp.
+trading',
          'a/b/hk/accts_transfermoney' => 'app-deployment.properties.h
+klcp.trading',
          'a/b/hk/userprereq' => 'app-deployment.properties.hklcp.trad
+ing',
          'a/b/hk/homeloggedmessage' => 'app-deployment.properties.hkl
+cp.trading',
          'a/b/hk/indices_us' => 'app-deployment.properties.hklcp.trad
+ing',
          'a/b/hk/accts_forms' => 'app-deployment.properties.hklcp.tra
+ding'
        };
[download]