The densities of divalent transition-metal chlorides in NN-dimethylformamide have been measured over the whole composition range at (283.15, 293.15, 298.15, 303.15, 313.15, 323.15, and 333.15) K. From these densities, apparent molar volumes and partial molar volumes of the salts at infinite dilution as well as the expansibilities have been evaluated. The apparent molar isentropic compressibilities of transition-metal chlorides in DMF have been determined from sound velocity data obtained at 298.15 K. The results have been discussed in terms of complex formation.