The diffusion couple technique is a valuable experimental approach in studying phase relations in multicomponent systems. The use of different modifications of the method is illustrated by examples of phase diagram determination in various ternary systems. It is also shown that a number of error sources may appear when multiphase diffusion experiments are employed for constructing isothermal cross-sections. The difficulties connected with the concentration measurement at the interfaces and problems associated with the formation of a quasi-equilibrated diffusion zone are discussed. It is demonstrated that the efficiency of the diffusion couple technique is very high. However, in order to increase the reliability of the information obtained about a ternary diagram, a combination of the diffusion methods with an investigation of selected alloys is desirable.