High-resolution velocity models developed using full-waveform inversion (FWI) can image fine details of the nature and structure of the subsurface. Using a 3D FWI velocity model of hyper-thinned crust at the Deep Galicia Margin (DGM) west of Iberia, we constrain the nature of the crust at this margin by comparing its velocity structure with those in other similar tectonic settings. Velocities representative of both the upper and lower continental crust are present, but there is no clear evidence for distinct upper and lower crustal layers within the hyper-thinned crust. Our velocity model supports exhumation of the lower crust under the footwalls of fault blocks to accommodate the extension. We used our model to generate a serpentinization map for the uppermost mantle at the DGM, at a depth of 100 ms (~340m) below the S-reflector, a low-angle detachment that marks the base of the crust at this margin. We find a good alignment between serpentinized areas and the overlying major block bounding faults on our map, suggesting that those faults played an important role in transporting water to the upper mantle. Further, we observe a weak correlation between fault heaves and serpentinization beneath the hanging-wall blocks, indicating that serpentinization was controlled by a complex faulting during rifting. A good match between topographic highs of the S and local highly serpentinized areas of the mantle suggests that the morphology of the S was affected by the volume-increasing process of serpentinization and deformation of the overlying crust.