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I did some research (luckily I speak Russian) and returned my own ticket, so here's how it works.
If you bought a ticket online, cancelling is simple. Login to the User Control Panel and go to the Ticket Return tab:
Enter the details of your electronic ticket and you should receive a refund within 2 weeks. Many people report getting their money within a single day, so it probably depends on your bank.
If you bought a ticket at a train station using cash, you need to go to a ticket office again for a refund. You don't have to visit the same ticket office, any Ukrainian Railways office can do it. At the Kiev Main Train Station there are separate windows for ticket returns ("повернення квитков").
To process the return you need your ID (ideally a passport) and the ticket itself. You fill out a short form and get your money back in cash.
If you bought a physical ticket using a credit card, it gets more complicated. Officially you're supposed to get your money back to the same card, however they're currently unable to process returns to foreign banks. Therefore I received my money back in cash, which was a pleasant surprise.
Again, bring your ID, fill out several forms, and get your money back.
When doing a return be aware of the following:
Returns processed more than 24 hours before departure only cost a small fee (around 2$). Returns processed later on carry a significant fee, so it's best to do it a day in advance. Returns after the departure of the train are impossible.
The ticket office employees speak zero English. Therefore I strongly recommend getting a ticket online in the first place.
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