Yes. If the card is a debit card then you are spending your own money. If it is a Credit Card then you spending the credit card companies money and you can quickly forget how you can repay that money back to the credit card company with interest
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You give me your account number, pin number and the CVN on the back of the card...that will definitely let me use your ATM card. But, I suppose you are asking how You use your own card to shop. Well, it is pretty much the same as I already told you. You fill out your order with your address, name, account and CVN and the merchant uses that information to withdraw funds from your account.
Now, I hope you noticed that you are giving a potentially complete stranger some very important information. You want to ensure that the merchant is trustworthy and that the information is protected by encryption. You also want to be sure that your computer is not infested with some virus or keylogger.
All-in-all, it is somewhat safer to perform the transaction by a proxy service such as PayPal.