Tetrakis(triphenylphosphine)palladium(0) catalyzes the highly regioselectiveaddition of phenyl thiocyanate (PhSCN) to terminal alkynes, which attains the simultaneous introduction of thio and cyano groups to the internal and terminal positions of alkynes, respectively. This reaction may proceed via the oxidativeaddition of PhSCN to Pd(PPh3)4, which forms Pd(SPh)(CN)(PPh3)2 as the key intermediate