There are a few options for you when buying Ukraine train tickets.
In both cases, however your trip is planned, the tickets will be booked through the computerized order system "Express-2". They are available at any Ukraine railway station or a ticket office, but there is a problem here. Unfortunately the computerized order system "Express-2" is not integrated into the Western European booking systems. Therefore tickets in Ukraine can only be booked inside the country.
Nevertheless the situation is not hopeless. You still have an opportunity to have your tickets booked in advance. There are a few Ukrainian travel agencies which can either arrange for you to collect tickets when you arrive in Ukraine or deliver them by DHL to your home. I recommend you to use the services of the reputable agency "Unipress". They will deliver your tickets within 4 business days.
You will find the Ukraine train schedule at the "Ukrzaliznitsa". web site (in Russian as well as Ukrainian).
Additionally, timetables for trains throughout the former Soviet Union can be found at "Poezda.net". (site in English). The most comprehensive site about train travel in Europe is presented at Deutsche Bahn. (available in English and German languages).
OK, you have bought your ticket after all this hard research! Now when you have it in your hands, let's check whether everything was done correctly. Here is your Ukraine train ticket. Check it carefully!

Practical information about Ukraine trains, their classes and sleeping accommodations is available at Ukraine Train Travel page.
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