The invention relates to catalytic microelectrolysis packing for treatment of pharmaceutical wastewater, heavy metal wastewater, printing and dyeing wastewater and the like. The catalytic microelectrolysis packing is spherical packing prepared from the following components in parts by weight: 90-95 parts of cast-iron scrap, 0-10 parts of aluminum and 0-5 parts of copper by means of weighing, mixing, melting and molding, wherein any one or both of aluminum and copper exist; the diameter of the spherical packing is 5-10mm; and the carbon content of the cast-iron scrap is 3-4 percent. The packing has the beneficial effects of overcoming inherent defects of easily caking, deflection and blockage of traditional microelectrolysis packing prepared from cast-iron scrap and improving the pollutant removal rate and wastewater COD removal rate, so that the biodegradability of wastewater can be improved.