The hydroesterification of cyclohexene is catalyzed by a preformed Pd(PPh3)(2)(TsO)(2) complex I in methanol as solvent. The effect of PPh3, TsOH, and water on the TOF has been evaluated. The system I/PPh3/TsOH = 1/6/8, in the presence of 800 ppm of H2O, at 373 K and under 2.0 MPa of CO leads to a TOF as high as 850 h(-1). The increase of TOF observed adding a hydride source such as TsOH and H2O suggests that Pd-hydride species plays a key role in the first step of the catalytic cycle. The initial reaction rate increases linearly with the concentration of cyclohexene and of MeOH and passes through a maximum with increasing the pressure of CO. The rate equation r(0) = k(1) P-CO (1 + k(2)P(CO) + k(3)P(CO)(2))(-1) fits well the experimental data. The values of k(1), k(2), and k(3) have been evaluated at different temperatures. From the plot In k versus 1/T, E-1 = 19.4 kcal/mol, E-2) = 20.6 kcal/mol and E-3 = 6.5 kcal/mol have been evaluated. On the basis of experimental evidences and of the kinetic study, a catalytic cycle mechanism has been proposed. (C) 2002 Elsevier Science B.V. All rights reserved.