Or maybe something like this:

my %table;
while (<DATA>) {
    chomp;
    my @f = split / \| /;
    my $i = 0;
    while(@f){
        push @{$table{$i}}, shift @f;
        ++$i;
    }
}

use Data::Dumper;
print Dumper \%table;

print "\n=>> Paths:\n", join $/, @{$table{4}};

__DATA__
This | Is | An | Entry | //Path/To/File.pdf
This | Is | Entry | 2 | //Path/To/File2.pdf
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