Our understanding of the nature and influence of TM-LA (Lewis acid) interactions has considerably improved and the scope of LA susceptible to behave as sigma-acceptor ligands has been significantly extended over the last 15 years. Nonetheless, the exact nature of TM-LA interactions is still a matter of debate and little is known yet about the precise impact of the coordination of LA to TM. Herein, we propose to explore Au complexes featuring phosphine-boranes and related ambiphilic ligands using XAS. Gold L-edge XAS will be applied as a direct experimental probe and the resulting data will be paralleled with theoretical calculations. Applications to TM/LA cooperative catalysis are envisioned.