Sewage sludge and polystyrene are considered very challenging for the waste management authorities in urban centers across the globe. In the current study, catalytic co-pyrolysis of the dewatered sludge (DS) and waste polystyrene (PS) was conducted. The co-pyrolysis of DS and PS; 60% polystyrene+40% dewatered sludge was concluded as optimum ratio with 11.21% higher energy production as compared with other compositions. The produced bio-oil were investigated having higher slags/wax and lower aromatics. Therefore, ZSM-5 (3% weight basis) catalyst was employed, and it had enriched the bio-oil quality, provided higher aromatic hydrocarbon yields with reduced wax and slag formation. To understand the thermodynamic behavior of all dewatered sewage sludge and polystyrene, detailed TGA analysis was carried out. The relative abundance of the aromatic hydrocarbons was identified by GC-MS and FTIR analysis. The synergist compositional analysis of the bio-oil and syngas was carried out by using artificial neural networking techniques. The aromatic components in bio-oil were found to have positive correlations when catalyst were employed. The proposed energy recovery model had capacity of generating 20,863 KWh/d of electrical energy, dealing 10 tons/d of biowaste: and leads the societies towards cleaner environment and positive contribution to bio-circular economy.