The invention belongs to the field of refractory materials, and relates to a magnesium-calcia-zirconia brick for a sintering zone of a cement kiln and a using method thereof. The brick is characterized in that the brick takes high-quality magnesite and synthetic calcium zirconate as main raw materials, and comprises the following raw materials in percentage by mass: 40 to 45 percent of coarse magnesite with the diameter of between 5 and 1 mm, 15 to 20 percent of medium magnesite with the diameter of between 1 and 0.088 mm, 15 to 20 percent of fine magnesite with the diameter less than 0.088 mm, and 15 to 25 percent of calcium zirconate with the diameter of between 1 and 0 mm; the magnesia content of magnesite is more than 96 percent; chemical components of the alcium zirconate are 60 to 65 percent of zirconia and 35 to 40 percent of calcia; and the mixed raw materials are added with a paper pulp waste liquid, and the mixture is calendered, pressed, dried and sintered at a temperature of more than 1,600 DEG C to obtain the magnesium-calcia-zirconia brick. The magnesium-calcia-zirconia brick zonally substitutes magnesia-chromite bricks in combination with the characteristics of chrome-free bricks according to different operation conditions of different cement kilns, maximizes favorable factors and minimizes unfavorable factors, improves the performance price ratio of refractory bricks for the sintering zones as much as possible, and realizes the chrome-free performance of the refractory bricks for the cement kilns.