I just noticed there are functions for this in List::Util: pairkeys and pairvalues. For example:

use v5.14;
use List::Util qw(pairkeys pairvalues);

my @a = qw(a b c d e f);
say "keys = ", join ", ", pairkeys @a;
say "values = ", join ", ", pairvalues @a;

my %h = @a;
say "keys = ", join ", ", keys %h;
say "values = ", join ", ", values %h;
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The obvious difference to keys and values of a hash is that pairkeys doesn't remove duplicates and it keeps the original array order.