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Petrochemical wastewater contains inhibitory compounds such as aromatics that are toxic to microorganisms during biological treatment. The compact and layered structure and the high amount of extracellular polymeric substances (EPS) in aerobic granular sludge (AGS) can contribute to protecting microorganisms from the harsh environment. This study evaluated the changes in the granule properties, pollutants removal, microbial metabolic potential and molecular microbial characteristics of the AGS process for petrochemical wastewater treatment. Granules treating petrochemical wastewater had a higher SVI 30 /SVI 5 value (0.94) than that treating synthetic wastewater. An increase in bioactivity and EPS secretion with higher bio-polymer composition, specifically the functional groups such as hydroxyl, alkoxy and amino in protein, was observed, which promoted biomass aggregation. The granules also had more than 2-fold higher specific oxygen utilization rate. The AGS-SBR process obtained an average COD removal of 93% during petrochemical wastewater treatment and an effluent bCOD of below 1 mg L−1. No obvious inhibition of nitrification and denitrification activity was observed in the processes attributed to the layered structure of AGS. The average effluent NH 4 +-N of 5.0 mg L−1 was obtained and TN removal efficiencies of over 80.0% was achieved. Molecular microbial analysis showed that abundant functional genera Stenotrophomonas and Pseudoxanthomonas contributed to the degradation of aromatics and other petroleum organic pollutants. They were enriched with the variation of group behavior while metabolisms of amino acids and carboxylic acids by the relevant functional genera (e.g., Cytophagia) were significantly inhibited. The enrichment of Flavobacterium and Thermomonas promoted nitrification and denitrification, respectively. This research revealed the rapid start-up, enhanced granule structural strength, high inhibition resistance and considerable performance of AGS-SBR for petrochemical wastewater treatment. [Display omitted] • AGS kept stability and high efficiency in petrochemical wastewater treatment. • Average COD removal of 93% and TN removal of over 80% were achieved. • High SVI 30 /SVI 5 and bioactivity with increased EPS secretion were observed. • Stenotrophomonas and Pseudoxanthomonas contributed to petroleum organic degradation. • AGS process showed significant potential for petrochemical wastewater treatment. [ABSTRACT FROM AUTHOR]