Ukraine is a big country that I have only seen one part of: the capital, Kiev. I first went there for a conference, didn't have the highest expectations up front and came away impressed looking forward to my next chance to visit: the architecture was more pleasant than I had expected, and I liked the people that I met. It also felt pretty cheap.
Ukraine seems to be leaning towards integration with Europe, and the European Union flag can be seen flying even though Ukraine isn't actually in the EU (and doesn't, at the time of writing, have a road map to joining the EU, however talks are happening). As a result, people from many countries can visit visa free (check before you travel).
Ukraine uses the Cyrillic alphabet, like Russian. There is the odd difference, but not many. Learning to read this alphabet is highly recommended, since street signs, even in the capital, will tend to just be written in Cyrillic. (It's easy enough to learn, especially given that most lowercase characters are just the uppercase ones but smaller).
English in the capital was not all that widely spoken, but it wasn't impossible to find Ukrainians who did speak it either. As a rule, younger people are more likely to speak English than older people. You can meet people who will speak it really quite well.
There is a distinct Ukrainian language. It's closely related to Russian (it's got an extra case, the vocative), and is spoken especially in the west of Ukraine. In the east, Russian is much more likely to be used, and in the capital it's 50/50. Speaking Russian in the west can, I've heard, not be the best of ideas, since some people can be fairly nationalistic there and not like to use it. I haven't been there yet to witness this first hand, however, so I don't know how much of an issue it really is, and I suspect there's probably a good chance that if it's the only language you and a Ukrainian speaker had some of in common, pragmatism would win over.
