The activation and potential dissociation of ethane mediated by small cationic gold clusters Au x + (x = 2-4) has been explored by infrared multiphoton dissociation (IR-MPD) spectroscopy and density functional theory (DFT) calculations. The calculations show that the interaction between the gold clusters and ethane is mainly governed by the mixing of the ethane CH 3 bond-forming orbitals-(CH 3) with gold d-orbitals. While the CC single bond appears to be unaffected, this mixing leads to the selective activation of up to two ethane C-H bonds and a reduction of the activation barrier for C-H bond dissociation to up to 0.82 eV, making the reaction kinetically feasible at room temperature. In agreement with this, experimental IR-MPD spectra of the complexes Au 2 (C 2 H 6) 2 + and Au 2 (C 2 D 6) 2 + reveal that the dominant product is one where a single ethane C-H bond is dissociated resulting in a complex which contains an ethyl group and a bridge-bonded H atom along with a second, adsorbed C 2 H 6 molecule. A similar C-H bond dissociation mechanism is theoretically predicted for the Au 3 (C 2 H 6) y + (y = 2,3) and Au 4 (C 2 H 6) y + (y = 2,3) complexes, albeit thermodynamically less favorable. IR-MPD spectra of Au 3 (C 2 H 6) y + (y = 2,3) and Au 4 (C 2 H 6) y + (y = 2,3) confirm the encounter product to be the dominant one, although the coexistence of isomers containing ethyl groups cannot be excluded. Various pathways for C-H bond activation are theoretically explored and the ethane activation mechanism is compared to the gold mediated activation of methane and ethylene. 65 spectra (I 0) in between successive FELICE pulses. The IR-MPD spectra shown in this contribution display the ratio 65