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The prime objective of the current research work was to understand the role of microwave-assisted pyrolysis for the upgradation of expanded polystyrene (EPS) waste into valuable aromatic hydrocarbons. Ethyl acetate solvent was used to dissolve the EPS to enhance the homogeneous dispersion of EPS with susceptor particles. Biochar obtained from the pyrolysis was used as a susceptor. The design of experiments method was used to understand the role of microwave power (300 W, 450 W, and 600 W) and susceptor quantity (5 g, 10 g, and 15 g) in the pyrolysis process. The pyrolysis was conducted till the temperature reached up to 600 °C, and this temperature was achieved in the time interval of 14-38 min based on the experimental conditions. The obtained average heating rates varied in the range of 15 to 41 °C/min to attain the pyrolysis temperature. The EPS feed was converted into char (~ 2.5 wt.%), oil (51 to 60 wt.%), and gaseous (37 to 47 wt.%) products. The specific microwave energy (J/g) was calculated to know the energy requirement; it increased with an increase in susceptor quantity and microwave power, whereas specific microwave power (W/g) was a function of microwave power and increased from 15 to 30 W/g. The predicted values calculated using the model equations closely matched the actual values showing that the developed model equations via optimization had a good fit. The obtained pyrolysis oil physicochemical properties including viscosity (1 to 1.4 cP), density (990 to 1030 kg/m 3 ), heating value (39 to 42 MJ/kg), and flash point (98 to 101 °C) were thoroughly analyzed. The pyrolysis oil was rich in aromatic hydrocarbons and it was predominantly composed of styrene, cyclopropyl methylbenzene, and alkylbenzene derivates., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)