I understand the answer, when you are comparing this two child family with all the other two child families.Given that you find a family with two kids and they aren't both girls,
you are twice as likely to find one of each, than you are of having
both boys.
Think about that for a while. Once the truth of that statement hits you, you'll understand the 2/3 answer.
But we aren't doing that with the original question. All we know is that the guy has two kids. One is a boy, and the other we know nothing about.