A novel electrocatalytic system was developed to realize one-pot conversion of organic pollutants into liquid fuels, such as methanol (CH₃OH) and ethanol (C₂H₅OH). The process combines the catalytic oxidation of organic pollutants with electrocatalytic reduction of CO₂. We first coupled the electrocatalytic process with SO₄^•− based advanced oxidation processes (AOPs) for the degradation of 4-Nitrophenol (4-NP) using a 3D-hexagonal Co₃O₄ anode. In this step, 4-NP was mineralized to CO₂ and then the CO₂ was converted into CH₃OH and C₂H₅OH by electrocatalytic reduction using a flower-like CuO cathode. Experimental results show the destruction of 4-NP (60 mL, 10 mg/L) can be as high as 99 %. And the yield of CH₃OH and C₂H₅OH was 98.29 μmol L⁻¹ and 40.95 μmol L⁻¹, respectively, which represents a conversion of 41.8 % of 4-NP into liquid fuels and the electron efficiency was 73.1%. In addition, we found that 3D-hexagonal arrays of Co₃O₄ with different morphologies can be obtained by adding different amounts of urea. Also, we investigated the formation mechanism of the novel 3D-hexagonal Co₃O₄ arrays for the first time. A mechanism was proposed to explain the electrocatalytic steps involved in the conversion of 4-NP to CH₃OH and C₂H₅OH and the synergetic effects between AOPs and electrocatalysis.