When you submit the form, the value is presented with debug_dump(), so strings are quoted and array values listed.
<?php
$items = array(
'A' => 'Item A',
'B' => 'Item B',
'C' => 'Item C',
'D' => 'Item D',
'E' => 'Item E',
);
$groups = array(
'B' => 'Group 1',
'C' => 'Group 1',
'D' => 'Group 2',
'E' => NULL,
);
$field = new form_field_select($form, 'Items');
$field->options_set($items);
$field->options_group_set($groups); // Just remove if you don't want to group the items
$field->label_option_set('');
$field->required_error_set('An item is required.');
// $value = $this->value_get();
// $value = $this->value_key_get();
?>