Ratio and accumulation of polychlorinated biphenyls (PCBs) in urban soils from three sites across street in Novi Sad (Serbia) were analyzed. Ten PCBs (PCB 8, 20, 28, 35, 52, 101, 118, 138, 153, and 180) were extracted using microwave-assisted extraction (MAE), solid-phase extraction (SPE) clean-up, and quantified by GC/MS technique. Since PCBs remain persistent and toxic for all living organisms, the main aim of this study is to emphasize the importance of ongoing monitoring, even more than three decades after their industrial ban on the middle-sized sites with ‘light’ industry in their surroundings. The results indicate that higher molecular weight compounds, such as PCB 138, PCB 153, and PCB 180, exhibited the highest mean concentrations (108–121 ng g⁻¹ dry weight (DW)), whereas low weight compounds (PCB 20, PCB 28, and PCB 101) were accumulated at lower levels (84–101 ng g⁻¹ DW). Variability among soil samples was statistically significant, particularly for PCB 35 and PCB 118, following ANOVA, that reflecting localized heterogeneity likely influenced by proximity to pollution emission sources, soil composition, and specific surrounded environmental drivers. The predominance of high weight PCBs aligns with their environmental persistence, bioaccumulative potential, and association with the most common PCB mixtures, while low weight compounds due to their faster volatilization and degradation into the soil. These findings underscore the importance of compound-specific assessments in urban soil pollution monitoring, as well as the ecological and human health risks posed by persistent PCBs, including endocrine disruption and neurotoxicity. Likewise, this study provides a baseline for targeted monitoring, risk assessment, and remediation strategies in urban environments, emphasizing the need for ongoing and long-term surveillance to track PCB fate and transport.