I think it's sometime in the last week, but it might vary from cat to cat, and I suppose it might start a little bit before that in case the kittens come early. The cat's human will be able to tell by feeling the underside of the cat, as there'll be a bag of milk filling up behind each of the cat's nipples.
It's usually in the last week of pregnancy- some never get milk at all before. Usually it comes sooner if she's had kittens before, but it depends on the cat...