This paper describes a new method for producing TiCl4 by chloridizing materials of high content CaO and MgO, in which a combined fluidized bed is used as a reactor to avoid agglomeration between particles caused by molten CaCl2 and MgCl2. The combined fluidized bed consists of at least a riser tube and a semi-circulating fluidized bed. Two kinds of high titanium slag, in which the total mass content of CaO and MgO is 2.03% and 9.09% respectively, are employed to examine the anti-agglomeration effect and the conversion of the materials when the temperature ranges are between 923.15K and 1073.15K, gas apparent velocity 0.7-1.1m.s(-1), and inlet amount of solid materials is 4.6-7.0kg.h(-1). It is found that the anti-agglomeration effect in the combined fluidized bed is satisfactory and the new method can achieve a TiCl4 production capacity of 14.0-75.4t.m(-2).d(-1) in relation to 25.0-40.0t.m(-2).d(-1) from the conventional bubble bed. Furthermore, low-temperature chloridization, for example, at 923K or 973K, can also be used to produce TiCl4 and avoid agglomeration.