Extracellular polysaccharides (EPS) of a copper-sensitive (Cus) and a copper-resistant (Cur) Pseudomonas aeruginosa strain were investigated in terms of their production, chemical nature and response towards copper exposure. The extent of EPS synthesis by the resistant strain (4.78 mg mg−1 cell dry wt.) was considerably higher over its sensitive counterpart (2.78 mg mg−1 dry wt.). FTIR-spectroscopy and gas chromatography revealed that both the polymers were acidic in nature, containing alginate as the major component along with various neutral- and amino-sugars. Acid content in the Cur EPS (480.54 mg g−1) was greater than that in the Cus EPS (442.0 mg g−1). Presence of Cu2+ in the growth medium caused a dramatic stimulation (approximately 4-fold) in EPS synthesis by the Cur strain, while in a similar condition, the Cus failed to exhibit such response. The polymer of the resistant strain showed elevated Cu2+ binding (320 mg g−1 EPS) compared to that of the sensitive type (270 mg g−1). The overall observations show the potential of the Cur EPS for its deployment in metal bioremediation.