And, indeed, this is more or less what I ended up using (mine populates a hash of hashes). I haven't discounted tye's idea of "fixing" Config::Ini, though...

For the record:

my $inifile='config.ini'
my %words;
my $section;

open (INI,$inifile) || die "Couldn't open '$inifile': $!\n";
my $section='DEFAULT'; # Somewhere to store the garbage
while (<INI>) {
    next unless /\S/;
    next if /^[;'#]/; # Ignore comments
    chomp;
    
    if (/\[(.+)\]/) {
        $section = $1;
    } 
    else {
        $words{$section}{$_}=1;
    }
}
close(INI);
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