I think some places are different but when I worked at Meijer and did them you had to have cash. There is also a fee to pay normally starting at $12 and going up depending on where you're sending the money so make sure you have extra to pay that.
Other than that you just fill out the info for you and the other person.
I have western unioned a couple of friends in need. All I did was call their 1-800 number and gave them my credit card/debit card info and it was all taken care of. Very simple.
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