The influence of V doping at Mn site on charge order and spin order of La0.3Ca0.7MnO3 system has been studied by the measurement of magnetization-temperature (M-T) curves,resistivity-temperature (ρ-T) curves and electron spin resonance (ESR) spectra of samples La0.3Ca0.7Mn1－xVxO3 (x=0.05,0.10,0.134,0.20).The results show that, when 0.05≤3≤0.134,charge ordering (CO) phase exists in the system,and the spin order of the system exhibits the serial changes of paramagnetism (PM)—charge ordering (CO)—antiferromagnetism (AFM) with the decrease of temperature.When x=0.20,the charge ordering melts,and the system exhibits second-entering-type spin glass behavior.