I buy stuff online all the time - do you mean buying from an individual instead of a vendor?
There's a major element of trust required. Basically,
1) You and the person agree to transfer the item (either by winning an auction or whatever).
2) You make a transfer to them with your paypal account and directed to their paypal account.
3) AFTER the money actually transfers - they ship you the product (that's where the trust comes in).
4) You receive your product.
In general, you're better off sticking with people who have good transaction histories (ebay lets you rate buyers and sellers for trustworthiness).
For more details, visit the ebay website and read their FAQ.
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