A probabilistic analysis was performed on soil arsenic concentration data from 4 brownfield sites at Beijing (Chaoyang and Haidian Districts), involved in environmental assessment studies. The available data sets were processed to provide a statistical characterization of the background populations and differentiate “anomalous data” from the natural range of variation of arsenic concentrations in soil. The site-specific background distributions and the existing wide-scale background values defined for the Beijing area were compared, discussing related implications for the definition of metal contamination soil screening levels (SSLs) in site assessment studies. The statistical analysis of As data sets discriminated site-specific background populations, encompassing 88% to 94% of the sample data, from outliers values, associated with either subsoil natural enrichments or possible anthropogenic releases. Upper Baseline Concentration (UBC) limits (+ 2σ level), including most of the site-specific metal background variability, were derived based on the statistical characterization of the background populations. Sites in the Chaoyang South District area had UBC values in the range 10.4–12.6 mg·kg^-1. These ranges provide meaningful SSL values to be adopted for As in local site assessment studies. Using the wide-scale background value for the Beijing area would have erroneously classified most of the areas in the subject sites as potentially contaminated.