Abstract: The powdered (La0.8Ho0.2)2/3 Ca1/3MnO3 nanocrystalline was synthesized by sol-gel technique. Thermal analysis (TG-DTA) and X-ray diffraction were employed to investigate the chemical reaction process and the structural forming process. The effects of the mole ratio of citric acid to total metal cation content, calcination temperature and time on the formation of perovskite structure were investigated. Structural analysis showed that the powdered phase remains perovskite structure and becomes perfect above 680°C. The resistance measurement was carried out with a conventional four-probe method, and the M-T curves of samples were monitored by the superconducting quantum interference device (SQUID) operated at 0.1 T magnetic field. The results showed obviously changes in the phase transition owing to partial replacement of La by Ho element in La2/3Ca1/3MnO3.