In this study, we tested the use of lichen biomonitoring techniques for the assessment of air quality disparities at the urban scale. We based our evaluation on the results of a previous lichen biomonitoring study carried out in Milan (Northern Italy), which estimates the contamination by potentially toxic elements (PTEs) and its distribution over the area, also providing an evaluation of the main emission sources. Therefore, we used the traditional methodologies for environmental justice assessment: the proximity-based and the distribution-based approaches. The workflow we propose is a data-driven selection of emission sources that contributes to overcoming the dichotomy between the two approaches and is now widely debated in the scientific community. A socio-economic deprivation index was elaborated for each census unit of Milan city and then related to the proximity of the emission sources previously selected. The results suggested that in the surrounding of industries and railways, the deprivation is higher, while the proximity of main roads is inhabited by wealthier populations. The distribution-based approach was run through a quantile regression analysis, and the outcome indicated that among the wealthier groups, an increase in contamination is followed by an increase in socio-economic deprivation, whilst among the deprived groups, people with greater economic opportunities tend, however, to live in worse air quality conditions due to the proximity of communication routes. This study poses the potential to review the classical methods of EJ assessment, providing a reliable workflow applicable in urban areas—the most vulnerable in terms of air quality disparities in the present and in the future. Keywords: environmental justice; lichen biomonitoring; air quality; life quality; urban environment.