We used spider webs as a particulate matter (PM) sampler to assess the possible health risk to the inhabitants of Legnica city (Poland). We aimed to find out if it is a useful material and could provide reliable information. We selected two spider families (Agelenidae and Linyphiidae) whose webs structure enhances the PM accumulation. The collected particles were analysed using a Scanning Electron Microscope equipped with Energy Dispersive X-Ray (SEM-EDX) and Inductively Coupled Plasma Mass Spectrometry (ICP-MS) which provided morphological and chemical information and allowed to indicate possible sources of pollution. The results showed that PM10, the fraction of particles smaller than 10 µm, was dominated by the particles of natural origin, while fine fractions were composed of diverse anthropogenic particles, whose origin can be connected with the activity of the copper smelter and in smaller quantity with the road traffic. The carcinogenic and non-carcinogenic health risk was assessed for these pathways: inhalation, ingestion, and dermal, for children and adults. The non-carcinogenic risk was very high (Hazard Index: HI > 1) both for children (Cu, Ni, Pb, Cd) and adults (Cu, As, Pb, Cd). Moreover, high carcinogenic risk (>10-4) was found in most of the sampling points. The study shows that spider webs are useful in biomonitoring of PM and can also be used for health risk assessment. In the studied region, it was found that the possible negative impact of air pollution on human health exists.