Polycrystalline samples of La0.67-xCa0.33MnO3 (x=0.00, 0.02, 0.06, and 0.10) with different vacancies in La3+-site were prepared by sol-gel method. The grain sizes of samples were observed by SEM. XRD results show that the samples are single phase of perovskite-type oxides. The Curie temperatures and the magnetic entropy change of the samples were studied by VSM. The influence of the vacancy concentration in La3+-site on their magnetocaloric properties has been investigated. The higher Curie temperatures close to room temperature and the larger magnetic entropy changes have been observed. The maximum magnetic entropy change, 2.78 J/(kg·K), is obtained near its Curie temperature (277 K) under the field of 1 T for La0.67-xCa0.33MnO3 (x=0.02) sample.