Strains of the genus Mucilaginibacter, belonging to the phylum Bacteroidetes, have been noted for exhibiting high genome plasticity and for the vigorous production of extracellular polymeric substances (EPS). Here we analyzed the composition and properties of EPS generated by M. rubeus P2, isolated from a gold-copper mine and exhibiting extremely high resistance to multiple heavy metals. Production of EPS increased significantly upon exposure to elevated concentrations of Cu(II) and Zn(II), but not Au(III). In addition, the EPS produced by M. rubeus P2 displayed extremely high bio-adsorption of As(III), Cu(II) and Au(III), but not of Zn(II). Moreover, EPS production in Mucilaginibacter rubeus P2 exposed to 1 mM of Cu(II) was 8.5 times higher than EPS production in the same strain without metal (loid)-exposure. These findings constitute the basis for a future use of these EPS-overproducing bacteria in bioremediation of heavy metal contaminated environments. The functional groups, especially –SH, CO, and N–H/C–N in the fingerprint zone of glutathione (GSH) and polysaccharides-like components of EPS, were the main components of EPS involved in both Zn(II) and Cu(II) binding and removal. Around 31.22% and 5.74% of Cu(II)-treated EPS was shown to exist as (CO) structures and these structures were converted into C–OH and O–C–O upon exposure to Cu(II), respectively. In contrast, (C–OH/C–O–C/P–O–C) groups in EPS were observed to be positively correlated to increasing concentrations of Zn(II) in strain P2. Furthermore, the complete genome of M. rubeus P2 helped us to identify 350 genes involved in carbohydrate metabolism, some of which are predicted to be involved in EPS production and modification. This work describes the first detailed biochemical and biophysical analysis of EPS from any strain of Mucilaginibacter with unique heavy metal binding properties. The results will be useful for a better understanding of how microorganisms such as M. rubeus P2 adapt to heavy metal polluted environments and how this knowledge can potentially be harnessed in biotechnological applications such as industrial waste water purification, bioremediation of heavy metal contaminated soil and beneficial plant microbe interactions. The toolbox provided in this paper will provide a valuable basis for future studies.