BaTiO3 (BT) nano powder was prepared via non-hydrolytic sol-gel (NHSG) method by using barium acetate, titanium tetrabutoxide as precursors, glycerol and ethanol as solvents. The samples were characterized by DTA-TG, XRD, FT-IR and TEM. The influences of heat treatment temperature on the morphology and the microstructure of powder were studied, and the mechanism of low temperature synthesis was discussed. In addition, the de-esterification action between the precursors was also described in detail. The results show that the formation of Ba-O-Ti bond in the xerogel via NHSG route is duo to the de-esterification polycondensation of barium acetate and titanium tetrabutoxide, which plays the key role in the low temperature synthesis of BT powder. With the temperature rising to 700 °C, BT nano powder with good dispersion and even size distribution can be acquired and the average particle diameter is about 25 nm. Overlow and overhigh heat treatment temperatures are both not beneficial to the preparation of BT nano powder.