The multiwall carbon nanotube-mollified electrode (MWCNT-ME) was fabricated and its electrocatalytic activity of refractory organic pollutants of coking wastewater was investigated. The surface morphology, absorption properties, and the electrochemical behavior of phenol and aniline at the MWCNT-ME were analyzed. Using ultraviolet-visible adsorption spectroscopy (UV-vis), Gas chromatography mass spectrometry (GC/MS), and chemical oxygen demand (COD) test, the electrochemical oxidation properties of refractory organic pollutants of coking wastewater using the MWCNT-ME and the IrSnSb/Ti electrode were analyzed. Compared with the powder adsorption media, the MWCNT-ME was proved to have weaker adsorption activity, which means electrochemical degradation is the decisive factor of the removal of organic pollutants. The MWCNT-ME shows high electrochemical reactivity with oxidation peaks of 0.18 A and 0.12 A for phenol and aniline, respectively. Under the same working conditions, the MWCNT-ME COD removal rate 51% is higher than IrSnSb/Ti electrode’s rate 35%. The MWCNT-ME has application potential of electrochemical oxidation of refractory organic pollutants of coking wastewater.