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There is no direct connection between Prague and Kiev.
09:57 Prague – 14:49 Vienna and 16:42 Vienna – 19:43 Kiev
Price from 165 euros
10:02 Prague – 20:17 Przemysl and 23:10 Przemysl – 11:25 Kiev
Price from 95 euros
Tickets can be ordered here (reserve the 2 trains separately). Reservations open 2–3 weeks before departure.
Hotels in Prague (Booking.com)
Hotels in Kiev (Booking.com)