Yes, as long as the order is still pending payment. To change the discount, choose Edit Discount/Financial Aid... from the order's Actions menu. To remove it, click the trash can icon on the discount line. Each order can have only one discount.
If you remove an item from the order, or reduce its quantity, the discount is recalculated automatically. A percentage discount keeps the same percentage of the new total, and a flat amount is reduced if it would be more than the new total.
Once an order has been paid, canceled, or refunded, its discount can no longer be changed.