Rhee holds degrees from Davis and Elkins College (B.A.), Louisville Presbyterian Theological Seminary (M.Div.), Yale Divinity School (S.T.M.), and Chicago Theological Seminary (D.Rel.).

Rhee worked for racial justice from the early 60s and continues today to work for peace and reconciliation between North and South Korea and for a peaceful engagement policy of the United States with North Korea. After serving 25 years in the Worldwide Ministries Division in the (PCUSA) as Middle East mission coordinator, Asia mission coordinator, and associate director of the division,  Rhee served as president of National Council of Churches in the U.S.A. from 1992-93, and as the Moderator of the 212th  General Assembly of the PC(USA) in 2000-01.  From 1998 until last year when he assumed his present position, he taught mission and evangelism, and Asian theology as a Distinguished Visiting Professor, and served as director of the Asian-American Ministry and Mission Center at Union Presbyterian Seminary.