Yes. Examples: 1) The man was on his way to work when he wrecked his car. 2) He was on his way to work when he received a phone call. Likewise you can say: 1) The man was on his way home from work when he wrecked his car. 2) He was on his way home from work when he received a phone call.

Yes that is fine. You may say; he/she is one his way to work. Absolutely no problem with it. Hope this helps