Bond activation at a transition metal centre is a key fundamental step in numerous chemical transformations. The oxidative addition of element-hydrogen bonds, for example, represents a critical step in a range of widely applied catalytic processes. Despite this, experimental studies defining steps along the bond activation pathway are very rare. In this work, we report on fundamental studies defining a new oxidative activation pathway: combined experimental and computational approaches yield structural snapshots of the simultaneous activation of both bonds of a β-diketiminate-stabilized GaH2 unit at a single metal centre. Systematic variation of the supporting phosphine ligands and single crystal X-ray/neutron diffraction are exploited in tandem to allow structural visualization of the activation process, from a η2-H,H σ-complex showing little Ga-H bond activation, through species of intermediate geometry featuring stretched Ga-H and compressed M-H/M-Ga bonds, to a fully activated metal dihydride featuring a neutral (carbene-type) N-heterocyclic GaI ligand.