By default the sort order for products in Magento is from old to new.
That is sometimes not wanted, especially if you are working with a “Latest Products” category.
To change the sorting from new to old you have to edit the file Toolbar.php in App/Code/Core/Mage/Catalog/Block/Product/List/.
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protected $_direction = 'asc';
and replace it with
protected $_direction = 'desc';
Please back up your files before replacing the existing one (you are working on the core here) and note that this is a system-wide change.
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