The protonolysis of C-Au bonds in [AuRL] organometallic complexes has been studied by calorimetry for 12 R groups. The experimental data have been combined with density functional theory calculations to obtain bond dissociation energy (BDE) values. The C-Au BDE values show a good correlation with the corresponding isolobal C-H BDE values. The heat released in the protonolysis of [AuRL] has also been measured for R = Ph and L = P(OPh)(3), PPh3, PMe3, PCy3, and IPr, and these values strongly depend on the trans influence of L because of the mutual destabilization of the L-Au and Au-C bonds. The enthalpies of the transmetalation reaction [AuR-(PPh3)] + SnIBu3 -> [AuI(PPh3)] + SnRBu3 for seven R groups have been measured and compared with those of the corresponding [AuR(PPh3)] protonolysis.