The study was carried out in the most industrialised region of southern Poland. Four areas were selected for the study: the vicinity of the Miasteczko Śląskie Zn–Pb-works (ZW; with three transects selected: A, B, and C), and the metalliferous waste heaps (H1, H2, H3). Samples were taken from the surface soil layer, while only mature silver birch (Betula pendula Roth) trees (3–4 m high) growing spontaneously in the study area were selected for the collection of leaves. The analysis of metals including trace metals (TMs; Ag, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Ni, Pb, Tl, and Zn) in the soil and leaves, as well as the contents of specialized leaf compounds belonging to polyphenols were performed. In general, the B. pendula trees in transects A and B located within 500 m of the furnaces exhibited 3–9 times higher content of TMs in their leaves compared to the plants located further away from the Zn smelter. In contrast, the quantity of TM in trees from transect C was independent of distance. The accumulation of TMs in the leaves was significantly lower in the metalliferous waste heap sites compared to the ZW area. It was hypothesised that the accumulation of TMs in B. pendula leaves would depend on the location and distance from the polluting source. It was demonstrated that TMs content in soil affects the accumulation of phenolic acids and flavonoids.