In order to rationalize enhanced HER activity of Rh-exchanged Ni surface, we turned to the analysis of H ads energetics on Rh-modified Ni surfaces. We studied Ni(111) and Ni(001) using DFT calculations, and to model modification by Rh, we added Rh in the surface or subsurface layer of these Ni(hkl), effectively modelling the surface of subsurface alloys. We find that surface incorporation of Rh is energetically more favored than subsurface inclusion of Rh on both Ni surfaces, in agreement with previous reports . In the case of Ni(111), surface incorporation of Rh is more favored by -0.20 eV, while this difference for Ni(001) is -0.11 eV. Considering that H ads energetics was shown to give the volcano-type relationship with HER activities in alkaline media , just like in acidic media , we used the methodology of Nørskov et al. to establish Tafel analysis performed on HER polarization curves of Rh-exchanged smooth Ni-poly