An activated carbon with ash content less than 10% and specific surface area more than 1 600 m2/g was prepared from coal and the effect of K-containing compounds in preparation of coal-based activated carbon was investigated in detail in this paper. KOH was used in co-carbonization with coal, changes in graphitic crystallites in chars derived from carbonization of coal with and without KOH were analyzed by X-ray diffraction (XRD) technique, activation rates of chars with different contents of K-containing compounds were deduced, and resulting activated carbons were characterized by nitrogen adsorption isotherms at 77 K and iodine numbers. The results showed that the addition of KOH to the coal before carbonization can realize the intensive removal of inorganic matters from chars under mild conditions, especially the efficient removal of dispersive quartz, an extremely difficult separated mineral component in other processes else. Apart from this, KOH demonstrates a favorable effect in control over coal carbonization with the goal to form nongraphitizable isotropic carbon precursor, which is a necessary prerequisite for the formation and development of micro pores. However, the K-containing compounds such as K2CO3 and K2O remaining in chars after carbonization catalyze the reaction between carbon and steam in activation, which leads to the formation of macro pores. In the end an innovative method, in which KOH is added to coal before carbonization and K-containing compounds are removed by acid washing after carbonization, was proposed for the synthesis of quality coal-based activated carbon.