A gaseous elemental mercury (Hg0) sampler was developed for the assessment of mercury (Hg) pollution from the air and utilised aluminium (Al) powder as the accumulation medium. The Hg sampler is presented as an alternative cost-effective sorbent that can be used for the assessment of Hg pollution in atmospheric air in areas where natural bio-indicators such as lichens and moss do not grow, including the urban environments. The chemical treatment of Al materials was necessary to weaken the aluminium oxide (Al2O3) layer to increase the adsorption capability of Al material. Treated Al samples were exposed to Hg vapours for one hour to two weeks in a Hg atmosphere chamber. Other Al powder samples were exposed to the ambient air at areas of the Tshwane Metropolitan Municipality for six to ten months. The analysis of samples by an RA-915+ Zeeman mercury analyser showed that the limit of detection (LOD) and limit of quantification (LOQ) for the determination of Hg in Al powder with a mass of 100 mg were found to be 0.31 ng g−1 and 1.0 ng g−1, respectively. The content of Hg that accumulated on Al powder was linear from 0.1 to 25 ng g−1, thus enabling the measurement of Hg accumulation from air at the global average concentration level. Mercury from air that accumulated on Al powder in the Tshwane Metropolitan Municipality ranged between 70 ng g−1 and 155 ng g−1.