PayPal will side with the buyer pretty much 100% of the time. I just dealt with a case where the buyer claimed to have not received two packages from us. After asking some questions to the buyer, he talked to his parents and found out they had put one of the packages in the recycling. He found that one, but still claims the other one never arrived. PayPal gave him his money back.
If you ship something expensive on eBay, make sure you use a tracked service, with signature verification. Then you should be covered.
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