Biowaste eggshells are a valuable source of calcium carbonate suitable for various applications. In this study, spherical vaterite and calcite calcium carbonate polymorphs have been synthesised from discarded eggshells by the precipitation technique at ambient temperature. The influence of initial salt concentration with different polyelectrolytes such as ethylene glycol (EG), polyethylene glycol (PEG, 600 and 6000), and poly(sodium 4-styrenesulfonate) (PSS) at various w/v% concentrations on the polymorph crystal formation of precipitated calcium carbonate (PCC) particles was studied. The results indicated that PCC crystals with spherical, star-shaped and yarn shaped morphologies can be obtained based on the concentration of calcium ions and the presence of different polyelectrolyte solution. At low salt molar concentration, PEG-6000 and PSS polyelectrolytes were found to promote the formation of spherical vaterite calcium carbonate particles with particle mean diameters of 5.05 μm and 2.17 μm, respectively. Furthermore, silver nanoparticles were also loaded into the PCC particles in situ, and the surface area significantly increased from 2.2813 m2 g−1 in untreated ground eggshells to 30.4632 m2 g−1 in PCC particles in the presence of PSS and silver colloid solution. The EDS mapping revealed the average wt% of silver atoms loaded in PCC particles in the presence of PSS polyelectrolyte was lower (1.44 wt%) than in the presence of PEG-6000 (4.27 wt%) due to the silver encapsulation possibility during the core–shell formation, as confirmed by SEM images. The silver nanoparticle-loaded PCC particles in this study can be incorporated into the polymer matrix and employed for antimicrobial food packaging or wound dressing application.