A novel and efficient approach to ortho‐trialkylstannyl arylphosphanes by the reaction of arynes generated in situ with stannylated phosphanes (R3SnPR2) is described. Concurrent CP and CSn bondformation occurs with high yields, and stannylated products are easily transformed into valuable ortho‐substituted arylphosphanes. The reaction features high efficiency, good regioselectivity, and excellent