A new form of diffusion coefficient termed as thermodynamic diffusion coefficient is introduced in this paper. Conventionally, diffusion coefficients are evaluated using concentration gradient as driving force. But truly, chemical potential gradient is the actual driving force that determines the material flow in any part of the system. Thermodynamic diffusion coefficients are based on chemical potential gradient as driving force. The relation between thermodynamic diffusion coefficients and phenomenological coefficients has been established. The advantages of thermodynamic diffusion coefficients have been underlined, especially, in the cases of line compounds where concentration difference across the phase is zero or in case of intermetallic compounds with narrow homogeneity range. The intrinsic thermodynamic diffusion coefficients are equal to tracer diffusion coefficients. This helps in estimating tracer diffusivities in cases where tracers are not easily available. The advantages of thermodynamic diffusion coefficients are shown in binary and ternary systems by illustrating them in Ni-Al and Fe-Ni-Cr systems.