prasadbabu,
You have misunderstood hashes. You should have a look at perldoc perldata. A hash can only have a single scalar as a value. The good news is that references are scalars, so you can have a reference to another data type such as an array. There are tied implementations such as Tie::Hash::MultiValue that would do this for you, but you can do it yourself too.

#!/usr/bin/perl
use strict;
use warnings;
my %hash;
my @pairs = qw(1 canada 1 us 2 england 3 france 3 russia);
while ( @pairs ) {
    my $key = shift @pairs;
    my $val = shift @pairs;
    push @{ $hash{$key} } , $val;
}
for ( sort keys %hash ) {
    print "$_ # ", join ', ' , @{ $hash{$_} };
    print "\n";
}
__END__
1 # canada, us
2 # england
3 # france, russia
[download]

Note: You would normally assign anonymous arrays to the keys as ccn shows. I did it this way to show how to add new elements after the initial hash is created a la push.