When God Ain't Lookin' is about the relationship of a young man, George and an older woman, Ann. George did not know of their difference in age nor the fact that Ann was studying to become a nun. The story spans both of their lives as they meet and part periodically throughout their lives. George is never quite able to forget about Ann. The story is further complicated by the fact that Ann has stolen money from the church. She was giving it to George. The setting for the story moves around the United States and Mexico before ending in Canada.