The invention discloses a material with reversible thermo-optic modulation characteristics. According to the invention, Na<2>CO<3>, Li<2>CO<3>, TiO<2>, Ba<2>CO<3> and Bi<2>O<3> are used as raw materials, and the material with reversible thermo-optic modulation characteristics is prepared with Bi<0.5>Na<0.5>TiO<3> and BaTiO<3> as main materials and LiBiO<3> as a doping material by using a solid-phase sintering process; the material has a chemical formula of (1-x) (Bi<0.5>Na<0.5>TiO<3>-BaTiO<3>)-xLiBiO<3>, and x in the formula is no less than 0.01 and no more than 0.909; and the material has thecharacteristic of photochromic response, can realize rapid coloring within 10 s, shows good reversibility, and can be decolored and return to an original state under the condition of thermal stimulation. The preparation method comprises the following steps: 1) preparation of raw materials; 2) pre-firing of the material; and 3) sintering of the material with reversible thermo-optical modulation characteristics. The invention has the advantages that the prepared material has the characteristic of photochromic response, can realize rapid coloring within 10 s, shows good reversibility, and can return to the original state under thermal stimulation at 180-200 DEG C for 10-30 min; synthesis steps are simple; the price of the raw materials is inexpensive; and additional colorants are not needed.