If like me you have a natwest card with no issue number you then just enter 0 or 00 or 000 depending on the site, natwest will pick up on this and ask you to enter some details from your card , they will then give you a username and you enter a passward you would like to use. This is what happend when I ordered some things from a website.
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When buying Skype credit on Internet
Its a sinvle digit on the front of the card. 1-9. Some bank cards don't use issue numbers such as RBS so if you are trying to pay for something online and they are asking for it just leave it blank if your card doesn't have one.
A number on a card.