Due to the low production cost and light weight, copper-clad aluminum conductors show great potential value in the field of power transmission, while the phase structure and organizational changes at the Cu–Al interface in high-temperature environments have a great impact on the electrical and mechanical properties. In this paper, Cu–Al diffusion couples are prepared to study the diffusion process, microstructure, and growth kinetics of intermetallic compounds (IMCs) in Cu–Al interface during heating from 600 °C to 800 °C, and the mechanical and electrical properties of Cu–Al diffusion couples are discussed. The results show that after heat treatment, IMC layers are formed at the Cu–Al interface and the Al-side is composed of CuAl and CuAl2, in which the CuAl phase transforms from long to thick dendrites with the increase of temperature, and finally grows into a “popcorn” form. The IMCs at the Cu–Al interface from the Cu side to the Al side are in the order of Cu3Al layer, Cu9Al4 layer, Cu3Al2 layer and CuAl layer, among which the Cu3Al2 layer is the thickest (168.42 μm at 700 °C), while the Cu3Al layer is the thinnest (37.32 μm at 700 °C). The kinetic calculations show that the diffusion layer grows up rapidly, which is caused by the generation of liquid-phase during the heating process, leading to the acceleration of the diffusion of Cu and Al. The kinetic factor of the Cu3Al2 layer is the largest (n = 0.69), causing the fastest growth rate of the Cu3Al2 layer, while the Cu3Al layer shows the largest activation energy for diffusion and the smallest diffusion rate (Q = 9.48 kJ/mol, D0 = 2.06 × 10−1 m2/s), therefore its growth rate is the slowest. Based on the thermodynamic calculations and the Cu–Al phase diagram, a growth mechanism of the Cu–Al interface is proposed, the formation sequence of IMCs at the Cu–Al interface is Cu9Al4, CuAl, Cu3Al2 and Cu3Al. The formation of IMCs layer at the Cu–Al interface leads to a significant increase in the hardness of Cu–Al samples (the hardness of the Cu3Al2 is 10 times higher than that of Cu) and an obvious decrease in electrical conductivity (the electrical resistivity of Cu–Al is 5 orders of magnitude higher than that of Cu), affecting its application in the electrical industry.