a lot of words in Russian and Ukrainian are similar, but Not all.
e.g. onion - лук (рус.) цибуля (укр.)
please - пожалуйста (рус.) будласка(укр.)
hour - час (рус.) година (укр.)
But if person know old language of east slavenian people - старославянский (церковнославянский)
he can understand ukrainian as well as russian and byelorussian.
There is different dialects of Ukrainian. east dialects is closer to Russian