You have to pass its values (which are array references) and dereference them (as you can see below, inside the map function, by prepending the @
symbol):
use Array::Utils qw(:all);
my %records = (a => [ qw/ A B C / ], b => [ qw/ C D E A / ], c => [ qw/ A C E / ],);
my @unique = unique(map {@$_} values %records);
print join(' ',@unique); #will print "A B C D E"