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Two types of coke are penetrated by different content of potassium (K) vapor using potassium-adsorption experiments. The K content of the alkalized coke is analyzed with inductively coupled plasma atomic emission spectrometry (ICP-OES). In order to explore the influence mechanism of K on the coke gasification, the industrial properties of alkalized coke samples are tested with standard method, while their gasification process is investigated by thermogravimetric analysis. It is found that the broken degree of coke structure after penetration by K vapor increases with the increase of K content, and a critical value near 5 wt% of K content may exist for the formation of coke fragment. The catalysis of K on coke gasification accelerates with the increase of K content, and reaches the limitation when the content of K exceeds 3.5 wt%. The catalysis of K vapor on coke gasification is mainly characterized by the reduced gasification temperature and the increased pre-exponential factor, which will increase the active carbon sites.