Caley is a general partner of KVP. He led investments in Rib-X, CVRx, CoTherix, QuatRx, Kai Pharmaceuticals and ViewRay. He is a board member of ViewRay, is a board observer at QuatRx Pharmaceuticals and CVRx, and was a board observer at CoTherix (acquired by Actelion).

Prior to becoming a venture capitalist in 2000, Caley received his M.D. from the University of California, San Francisco, with honors. During medical school, he ran a research program investigating the genetic causes of deafness and the application of gene therapy to treatment of hearing loss. The findings were published in leading journals including Nature Genetics.

After medical school, Caley completed a general surgery internship at the University of California, San Francisco. He received an A.B. magna cum laude from Harvard College.