The deposition behavior and structural and magnetic properties of electroless Co-B and Co-Fe-B deposits, as well as the amorphous ribbon substrates, were investigated. These Co-based alloy deposits exhibited characteristic polycrystalline structures and surface morphology and magnetic properties that were dependent on the type of amorphous substrates. The catalytic activity sequence of the amorphous ribbon electrodes for anodic oxidation of DMAB was estimated from the current density-potential curve in the anodic partial electrolytic bath that did not contain the metal ions. Both the deposition rate and potential in the initial region were obtained in order of the catalytic activity, depending on the alloy compositions of the substrates. The deposition rate linearly varied against the deposition time. The initial deposition potential may have also determined the structural and magnetic properties of the deposit based on the thickness of μm order. Furthermore, a basic study of the electroless deposition processes on an amorphous ribbon substrate has been carried out in connection with the structural and magnetic properties of the deposits.