The effects of disordered structure on the thermal and electrical properties of Fe‐Co‐P‐B‐Si amorphous alloy are presented. From the X‐ray diffraction (XRD) pattern of series of Fe‐based amorphous ribbon alloys Fe80‐xCox P12B4Si4(x = 20, 25, 30, 35), all samples show amorphous structure. The good glass forming ability of those series samples is detected by differential scanning calorimeter (DSC) measurements. The electrical resistivity and its temperature dependence behaviour have also been measured by four probe method, which shows that an electron‐phonon interaction of disordered structure plays an important role on the resistance changes. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)