Catechol is a substance that is commonly found in wastewaters from a variety of sectors including paper, paint, petroleum, dyes, antioxidants, pesticides, iron and steel, solvents, nylon, detergent, textile, plastic, rubber, cosmetics, and medicine. In this study, sequential electrochemical and chemical multi-polymerization of catechol was investigated for environmental pollution abatement. The effect of operating parameters like catechol concentration (2–10 g/L), ammonium persulphate (APS) concentration (2–10 g/L) and reaction temperature (20–60 °C) were evaluated using response surface methodology. Catechol concentration was determined using HPLC in a gradient mobile phase. The electrochemical behavior of the polymer was investigated by cyclic voltammetry (CV). The structural and morphological properties of polycatechol were characterized by Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy with energy dispersive X-ray (SEM–EDX) analysis. It was observed from the SEM images a polymeric structure developed from a crystalline and heterogeneous structure when the APS concentration increased. Similarly, it was seen in SEM images that the polymers transitioned from a bulk and heterogeneous structure to a homogeneous structure as the temperature increased, and back to a heterogeneous structure as the catechol concentration increased. It was also found that catechol removal increased and reaction selectivity decreased by increasing the reaction temperature. The optimum operating conditions were found as 4 g/L catechol concentration, 9.5 g/L APS concentration, 30 °C reaction temperature with 100 cycles at 50 mV/s of electrochemical polymerization and 72 h of chemical polymerization. The results of this study show the potential of challenging new routes not only facile polymerization of organic monomers but also to decrease the undesirable pollutant concentration in the wastewater.