The microstructure, mechanical and electrical properties of cold-drawn thin layer copper cladding steel (CCS) wires annealed after different processes were studied by optical microscopy, electron omnipotent material experiment machine, micro hardness machine, SEM and electrical resistivity measurement system. The results indicated that the recovery and recrystallization of steel-core happened in the temperature range 550–750 °C for the holding period of 120 min. When the annealing temperature was higher than 750 °C, grains begun to grow and grain sizes increased gradually with increasing the annealing temperature. The tensile strength and micro hardness were declined with increasing annealing temperature and holding time. The distance of Cu–Fe atoms interfacial diffusion of thin layer CCS wires ranged from 4 µm of cold-drawn wire to 7.5 µm of annealed wire at 850 °C for 120 min. The higher the annealing temperature become, the larger the distance of Cu–Fe atoms interfacial diffusion is. When the annealing temperature was lower than 650 °C, the resistivity was slightly less than 71 × 10−3 Ω mm2 m−1 which was the resistivity of cold-drawn wire. When the annealing temperature was higher than 650 °C, the resistivity increased with increasing the annealing temperature. Meanwhile, the variation of electrical property of thin layer CCS wires was analyzed and discussed based on microstructure and interfacial diffusion.