Yes, you would be able to get an array of sockets.

To make them usable, you would need to use either non-blocking reads, or threads.

Here is your code made more readable/idiomatic/perlish:

use strict;
use IO::Socket;
#use Win32::SerialPort;

$|++;

print "how many? ";
my $PortCount= <STDIN>;
chomp $PortCount;

my (@sockinfo, $buffer);

for (1..$PortCount){
   my %sock;
   print "ip? ";
   $sock{IP} =<STDIN>;
   chomp($sock{IP});
   print "port? ";
   $sock{PORT}=<STDIN>;
   chomp($sock{PORT});
   push @sockinfo, \%sock;
}



foreach(@sockinfo){
 ## print "Opening Socket to ",$_->{IP}," port ", $_->{PORT},"\n";
  $_->{SOCKET}= IO::Socket::INET->new (PeerAddr=>$_->{IP},
                                    PeerPort=>$_->{PORT}, Proto=>'tcp'
+)
                 or die  "Can not connect: $@ \n  IP=" . $_->{IP}
                           . " Port=" . $_->{PORT};
  $_->{SOCKET}->recv($buffer,1024);
  print $buffer;
}
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