Alkoxycarbonyl(cyano)palladium(II) complexes trans-Pd(COOR)(CN)(PPh3)(2) (1, R = Me; 2, R = Et; 3, R = Pr-n; 4, R = Pr-i; 5, R = Bu-n; 6, R = Bu-t; 7, R = Bn) are prepared via oxidative addition of the corresponding cyanoformates to Pd(PPh3)(4) in toluene at room temperature or 50 degrees C and characterized by means of NMR (H-1, C-13{H-1}, and P-31{H-1}) and IR spectroscopy as well as elemental analyses. X-ray crystallography of 3, 4, and 6 showed a square-planar coordination around the Pd center that is bonded to alkoxycarbonyl and cyano ligands in the trans configuration. The Pd-CN and Pd-COOR bonds in 1, 3, 4, and 6 are similar to those of the cyanopalladium(II) and alkoxycarbonylpalladium(II) complexes reported to date. On reaction of Pd(PPh3)(4) with phenyl cyanoformate a thermally induced ligand exchange takes place to afford the dicyanopalladium(II) complex, trans-Pd(CN)(2)(PPh3)(2) (8). Complex 2 is able to catalyze the reaction of norbornadiene with ethyl cyanoformate to produce (2R*,3S*)-ethyl 3-cyanobicyclo[2.2.1]hept-5-ene-2-carboxylate (13) and is recovered after the reaction. This observation supports the identification of alkoxycarbonyl(cyano)palladium(II) complexes as intermediates in the catalytic cycle of cyanoesterification of norbornene derivatives.