The invention belongs to the technology field of oxide thermoelectric materials of the functional materials and the preparation thereof, and relates in particular to thermoelectric materials of acetate doping with co-o-Na. The invention utilizes sol-gal method, takes the acetate as the raw material and the citric acid as the complexing agent. The sol is formed at the temperature of 353 K to 363K and the xerogel is formed at the temperature of 323 K to 393K. The precursor nano meter powder can be obtained by gel pyrolysis and roasting; and the bulk material can be got by sintering finally. Theinvention utilizes the common water metal acetate as the raw material and the whole preparation process does not produce poisonous and harmful gas. The synthesis technology is simple and safe; furthermore, the drying process adopts decompression drying and realizes the drying process with low temperature and short time; also, the precursor powder has good uniformity and obvious layered structure,which is helpful to producing the bulk thermoelectric materials with high crystal orientation and high performance.