Single crystals of La0.67Ca0.33MnO3 and La0.67Ca0.33Mn0.96Fe0.04O3 were obtained by floating zone method.Laue diffraction pattern and rocking curve of the single crystals show that their quality is good. The magnetic behaviours of these compounds have been studied. Fe doping significantly depresses the magnetic contribution to the total specific heat Cp, but slightly influences the lattice contribution at temperatures above 50K. The peak of CP shifts towards high temperatures with increasing magnetic field. Both single crystals exhibit the first-order magnetic transition around the Curie temperature.