Following-up on benn's method of:

  %item = %{$array[0]}; # Creates a copy of the hash
  print $item{key};
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You could do that cheaper using TypeGlobs (Just showing off recently-acquired knowledge).

  no strict "vars"; # Allow local decs
  local *item = \%{$array[0]}; # Creates a ref. No copy.
  print $item{key};
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Details in perldoc perldata, under "Typeglobs and Filehandles".