Chlorine content in the MSW incineration ash and coal is a critical factor in considering the design and operation of incinerator and power plant et al. because HCl gas emitted from the plants causes not only air pollution but also the corrosion of plant. Chemical method for the determination of chlorine content in the solid samples is the most common approach, but it is mostly applied to the determination of low concentration of chlorine content in the sample. So standard method is needed to measure the high concentration of chlorine content of solid samples. Eschka method which is based on the ASTM (D 2361-85) can be used to determine chlorine content in coal, but it is not sure that it can be applied to measure the high concentration of chlorine content of solid samples. For this, determination of chlorine contents by Eschka method was carried out by using pure reagents having high chlorine content, and the results were compared as the basis of theoretical and experimental values. Also MSW bottom and fly ashes, PVC and coals were selected for determination of chlorine content by Eschka method. Eschka method with potentiometric titrator can be measured high concentration of chlorine contents by controlling titrant's concentration. Based on the test results of various kinds of solid samples, the Eschka method is more recommended in the measurement of chlorine content in MSW incineration ashes and coals.