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It depends if the seller set the purchase as pay immediately. If so, when you hit "buy it now", you'll pay for it instantly. There's also a setting on Paypal, which asks you if you want to skip the log in to "pay now", if you've clicked this, its essentially one click purchase the same as with Amazon.
Muppetteer
Whenever I've bought anything, the purchase and the payment were separate.
Perhaps it's because of the value?