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Background: Novel eco-friendly silver nanocomposites of xanthan/chitosan biguanidine hydrochloride polyelectrolyte complexes were successfully prepared.Methods: Silver nanoparticles (AgNPs) were formed through an insitu eco-friendly reduction by the non-toxic polysaccharides without the usage of toxic reagents. FTIR confirmed the successful preparation of the nanocomposites while XRD confirmed the presence of AgNPs with face-centered cubic structures. TEM confirmed the homogeneous distribution of AgNPs with an average size of 14.1 nm. SEM was used to study the surface morphology of the nanocomposites while the energy-dispersive X-ray spectroscopy (EDX) confirmed the presence of AgNPs.Results: Thermogravimetric analysis showed that the thermal stability was improved in the presence of AgNPs as detected from the calculated integral procedure decomposition temperature. Antibacterial activity against different bacteria species was significantly improved upon increasing the content of AgNPs.Conclusion: Due to their interesting properties, the prepared polyelectrolyte complexes and their AgNPs nanocomposites could be employed potentially in many biomedical applications like drug delivery.