New chemical-state-specific scanned-energy mode photoelectron diffraction experiments and density functional theory calculations, applied to CO, CO/H, and N2 adsorption on Ni(100), show that chemisorption bond length changes associated with large changes in bond strength are small, but those associated with changes in bond order are much larger, and are similar to those found in molecular systems. Specifically, halving the bond strength of atop CO to Ni increases the Ni-C distance by 0.06 A, but halving the bond order (atop to bridge site) at fixed bond strength causes an increase of 0.16 A.