Although the wireless power transfer (WPT) system for electric vehicles (EVs) provides numerous advantages, there is still a low coupling coefficient and the misalignment between the primary coil and the secondary coil needs to be solved. In this paper, the transmission efficiency and transmitted power were calculated based on Series-Series (SS) compensation topology. The coupling coefficient is related to the coil parameters and misalignments. A simulation study was carried out to explore the variation in the coupling coefficient for different coil configurations under different air gaps and coil misalignments. Moreover, the influence of the internal parameters of the square coil on the coupling coefficient was further studied. Finally, this paper discusses the influence of ferrite cores with a square coil on the coupling coefficient. The results of this paper show that designing the optimal internal parameters of the square coil and the ferrite core can increase the coupling coefficient between the coils, which can also provide guidelines for the design and optimization of the magnetic coupling coils for a wireless charging system for electric vehicles.