This used to be possible with Western Union. The other party would go to the WU kiosk and pick up dollars. But now they started converting to UAH automatically, which gives a much worse rate than what you'd get in the black market. Likely the government/banks are reaping large profit with this new policy. But is there a way around it?
Edit: I found a workaround that supports cash payouts in USD -- Xoom by Paypal.