Coking wastewater is the poisonous wastewater with complicated components produced in the coking process and it is difficult to be degraded. The paper studies the static treatment effect of metallization pellet with high carbon (MPHC), sponge iron, 45＃steel chips and cast iron chips on coking wastewater. And the four substances are characterized by scanning electron microscope (SEM). The results indicate that the degradation performance of MPHC on coking wastewater is higher than that of sponge iron, 45＃steel chips and cast iron chips. There are abundant pores on MPHC, and the activated carbon has strong adsorption capacity, and it can adsorb the organic pollutants on the surface of primary battery, and promotes the progress of iron-carbon internal electrolysis reaction.