La0.67Ca0.33MnO3 perovskite-type manganite was synthesized by high-energy ball milling raw oxides of La2O3 (purity 99.9%), CaCO3 (purity > 99%), and MnO (purity > 99%). The ratio of ball and powder weight was 10:1 and the rotating speed was set to 500 rpm. X-ray analysis indicated that La0.67Ca0.33MnO3 single phase was formed completely when milling time is up to 4 h. The peak intensity of perovskite structure decreased and a hump-like peak appeared with further milling time. When the milling time is longer than 40 h, the perovskite structure disappeared and the amorphous phase was formed completely. Scanning electron microscopy picture of 24 h milled sample showed that the particle size generally vanes in a broad range from nanometer scale to a few pm. The magnetic measurements showed that ball milling samples have an inhomogeneous magnetic state and exhibit spin-glass like behavior. The significantly small magnetic entropy change and a remarkably broad temperature interval in entropy change were attributed to high degree of structural and magnetic disorder and broadening of magnetic transition.