A detailed analysis of the C(sp3)−H activation process by vinylidene AuI complexes is described based on an intrinsic bond orbital analysis. Based on our analysis this event can be divided into three phases: (i) hydride transfer, (ii) C−C bond formation, and (iii) σ to π rearrangement of the lone pair coordinated to Au. Small perturbations of the system lead to either a concerted asynchronous reaction, or a stepwise reaction featuring an intermediate with a C‐H‐C three‐centre two‐electron (3c–2e) bond. The role of π‐donating substituents is highlighted and provides a way of controlling reactions of this type in future experimental studies. Detailed theoretical investigations reveal that C(sp3)‐H activation by vinylidene AuI complexes proceed either by a concerted asynchronous or a stepwise reaction featuring a C‐H‐C three‐centre two‐electron (3c‐2e) bond. Intrinsic bond orbital analysis uncovers that this type of reaction is greatly facilitated by π‐donating substituents.