Environmentally green synthesis of stable polyvinyl pyrrolidone (PVP)-capped silver nanoparticles (PVP-AgNPs) was successfully carried out. The present study focused on investigating the influence of adding PVP during the synthesis process on the size, optical properties and antibacterial effect of silver nanoparticles produced. An aqueous extract of Eucalyptus camaldulensis leaves was used as a reducing agent. The effects of different PVP concentrations and reducing time on the synthesis of nanoparticles (NPs) were characterized by UV–Vis spectrophotometry, scanning electron microscopy (SEM), energy dispersive spectrum (EDX), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) and nano tracker analysis (NTA). The addition of PVP was studied. The prepared PVP-AgNPs were spherical with an average size of 13 nm. FTIR analysis confirmed that PVP protects AgNPs by a coordination bond between silver nanoparticles and both N and O of PVP. DLS results indicated the good dispersion of silver nanoparticles. PVP-AgNPs were found to be stable for nearly 5 months. Antibacterial studies through the agar well diffusion method confirmed that silver nanoparticles synthesized using PVP had no inhibitor activity toward Gram-positive and Gram-negative bacteria as opposed to silver nanoparticles prepared without adding PVP, which showed a significant antibacterial activity towards some of the tested pathogens.