The coexistence of multi-component dissolved organic chemicals causes tremendous challenge in purifying petrochemical wastewater, and stepwise selective adsorption holds the most promise for enhanced treatments. This study is designed to enhance the removal of multiple dissolved organic chemicals by stepwise adsorption. Special attention is given to the selective removal mechanisms for the major pollutant N,N-dimethylformamide (DMF), the sensitive pollutant fluorescent dissolved organic matter (FDOM) and other components. The results indicated that the combination of coal activated carbon and aluminum silica gel produced a synergistic effect and broke the limitation of removing only certain pollutants. Combined removal rates of 80.5 % for the dissolved organic carbon and 86.7 % for the biotoxicity in petrochemical wastewater were obtained with the enhanced two-step adsorption. The adsorption performance of both adsorbents remained stable even after five cycles. The selective adsorption mechanism revealed that hydrophobic organics such as DMF was adsorbed by the macropores of coal activated carbon, while the FDOM was eliminated by π-π stacking, electrostatic interaction and hydrophobic interaction. The hydrophilic organics were removed by the mesopores of aluminum silica gel, the silica hydroxyl groups and hydrophilic interaction. This study provides a comprehensive understanding of the selective adsorption mechanism and enhanced stepwise removal of multiple pollutants in petrochemical wastewater, which will guide the deep treatment of complex wastewater.