Stability of Pd-Co-Ni-Cu-P metallic glass was investigated in terms of free energy using first principle cluster calculations, thermal analysis, and photoemission spectroscopy measurements. We found that the internal energy of the Pd-based metallic glasses is dominated by the electronic structure near the Fermi level. The analyses on the electronic structure and local atomic arrangements indicate that the substitution of cobalt or a hypothetical atom Co0.5Cu0.5 for nickel in the Pd40Ni40P20 metallic glass decreases the free energy of the Pd-Ni-P metallic glass by increasing entropy without altering significantly internal energy. On the basis of the idea mentioned above, we prepared Pd28Co24Ni24P24, Pd25Co25Ni25P25 and Pd40Co40/3Ni40/3Cu40/3P20 metallic glasses. These metallic glasses certainly showed the nearly highest T
X, which directly reflect the activation energy against crystallization, among the Pd-based metallic glasses ever reported.