The invention discloses A-site high-entropy perovskite oxide MeTiO3 thermoelectric ceramic and a preparation method thereof. The A-site high-entropy perovskite oxide MeTiO3 has a single-phase perovskite structure, the elements in the A-site high-entropy perovskite oxide MeTiO3 are uniformly distributed without agglomeration, and the A-site high-entropy perovskite oxide MeTiO3 has thermoelectric performance and can be used in the field of thermoelectric materials. The chemical composition of the A-bit high-entropy perovskite oxide MeTiO3 is (Ca < 0.2 > Sr < 0.2 > Ba < 0.2 > La < 0.2 > Pb < 0.2 >) TiO3, (Ca < 0.25 > Sr < 0.25 > Ba < 0.25 > La < 0.25 >) TiO3, (Ca < 0.25 > Sr < 0.25 > Ba < 0.25 > Pb < 0.25 >) TiO3, (Ca < 0.25 > Sr < 0.25 > Ba < 0.25 > Nd < 0.25 >) TiO3, (Ca < 0.25 > Sr < 0.25 > Ba < 0.25 > Sm < 0.25 >) TiO3, and (Ca < 0.25 > Sr < 0.25 > Ba < 0.25 > Eu < 0.25 >) TiO3. According to the invention, the high entropy of the perovskite structure is realized, the disorder degree of atom arrangement in the material composition is improved, the phonon scattering is increased, and the thermal conductivity is reduced, so that the thermoelectric performance is improved. In the sintering process, oxygen atoms are migrated and discharged through oxygen vacancies in material crystal lattices, the porosity is reduced, the ceramic density is improved, meanwhile, the oxygen vacancy concentration is improved, and the carrier concentration of the material is improved. By adopting a reduction annealing process of argon and carbon powder, the semiconduction of perovskite oxide is realized, the carrier concentration of the ceramic is improved, the conductivity is improved, and the thermoelectric performance is further improved.