That's built by this function: zen_get_country_list(), via this part of the tpl_modules_checkout_new_address.php template file:
Code:
<label class="inputLabel" for="country"><?php echo ENTRY_COUNTRY; ?></label>
<?php echo zen_get_country_list('zone_country_id', $selected_country, 'id="country" ' . ($flag_show_pulldown_states == true ? 'onchange="update_zone(this.form);"' : '')) . (zen_not_null(ENTRY_COUNTRY_TEXT) ? '<span class="alert">' . ENTRY_COUNTRY_TEXT . '</span>': ''); ?>
It pulls all the countries from the database. If you want to do something else with it, you'll have to write your own new function or new code to create your own pulldown list.
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