We have carried out first-principles calculations of H adsorption on Pd(211) using density-functional theory with the generalized gradient approximation in the plane-wave basis to find out that the most preferred is the threefold hollow site on the terrace of Pd(211) with an adsorption energy of : the hcp and fcc sites being almost energetically equally favorable. For subsurface H adsorption on Pd(211), the octahedral site with an adsorption energy of is slightly more favorable than the tetrahedral site . Our calculated activation energy barrier for H to diffuse from the preferred surface site to the subsurface one on Pd(211) is , as compared with on Pd(111). Thus, there is an enhancement of the probability of finding subsurface hydrogen in Pd(211). Additionally, we find the diffusion barriers for H on the terraces of Pd(211) to be , while that along the step edge to be only and that within the second layer (subsurface) to be .