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I've just taken an order from a new customer (b2b) to make a delivery next week. The new customer asked me to use a purchase order number. What do I do with the purchase order number? Should I just put it on the delivery note and invoice?
Assuming you have already agreed a credit account for this customer, then the earlier advice is sound.
If, however, they don't have a credit account you should be careful. Remember the sale is not finished until you get paid. You could always send them a pro-forma invoice so that they can pay up front or ask for COD if it as an actual product that they have ordered.
It is not usual, in my experience, to expect a new supplier to automatically give credit without prior discussion.