This study evaluated relationships between the serpentine soil from a waste-rock dump of the abandoned Libiola sulphide mine (NW Italy) and its pioneer vegetation. We identified the tolerance of various species to environmental conditions and evaluated physical or chemical factors that influenced the first plants to colonize this stressful environment. Thirteen sampling sites were identified in the rock dump from characterization of surface or near-surface oxidation zone and vegetation type. Sampling sites were analyzed for slope, pH, mineralogy, soil chemistry, floristic composition, and the percent coverage of each species. In all the plots, species richness and vegetation cover were extremely low. The flora showed an acidophilous character.