The pronoun who refers to people; which refers to things.
See also:
- Using the Different Forms of Pronouns
- "Which," by James Thurber
- Who and Whom
- Whoever and Whomever
- Wh- Words
Examples:
- The man who just left drives a Pacer, which once was called "the car of the future."
- "An association of men who will not quarrel with one another is a thing which has never yet existed, from the greatest confederacy of nations down to a town meeting or a vestry." (Thomas Jefferson)
Practice:
(a) Nan's book, _____ was published in May, is now a bestseller.
(b) A writer is a lucky person _____ has found a way to talk without being interrupted.

