I too have been looking into this, here's a snippet from their FAQ:
I've sent a payment to the wrong mobile phone number ? what should I do next?
You must let us know immediately if you send a payment to the wrong number. If the money has been paid to someone with a Barclays current account, we will attempt to take the payment out of their account and return it to you. If the payment was to someone who holds an account with another bank, we will attempt to recall the payment.
If we are unable to recover the payment for you, for example because the payee no longer has funds in their account or refuse to return it, we may on request provide you with the payment details to enable you to contact the beneficiary bank yourself to help you recover the payment.
Please remember that you should always ensure you enter the correct details when making a payment, as we are not responsible if you send it to the wrong person. Each time you make a payment with Barclays Pingit, you will be shown a confirmation page before your payment is sent, so make sure to check these details are correct before you confirm.
I believe this means that if you have a non-Barclays account, they will attempt to reverse the payment like you can with BACS. I'm not sure on the timescales but I don't think you can hold out much hope if it's just an hour you're with him and he gets straight on the phone afterwards to cancel it. Problems might occur if he does it a lot, his bank might start asking questions re fraud.
If I was going to go down this route I would get him to send me a text from that phone with my name on it confirming services received, that way at least I would have something to go to the bank with as proof.
I guess the proof is in the pudding on this one.