ほぼ問題ないように見えますが、左外側の結合にもcategory_idを割り当てる必要があります。それ以外の場合は、アイテムのすべての注目アイテムを取得します:
SELECT i.*, category.name, category_feat_item.item_id AS featured
FROM item AS i
INNER JOIN item_category ON i.id = item_category.item_id
INNER JOIN category ON category.id = item_category.category_id AND category.id =1
LEFT OUTER JOIN category_feat_item ON i.id = category_feat_item.item_id AND category_feat_item.category_id = 1
ORDER BY featured DESC