Herein we report the facile synthesis of three dimensional macroporous (MP) silver monoliths serving as intelligent biomaterials against Gram negative (Escherichia coli, Salmonella typhimurium) and Gram positive (Bacillus subtilis) bacteria with more efficacy against Gram negative bacteria. The macroporous silver monoliths were examined by Fourier transform infra red (FTIR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD) study, field emission scanning electron microscopy (FESEM), energy dispersion X-ray spectroscopy analysis (EDX) and Brunauer–Emmet–Teller (BET) adsorption technique. From the antibacterial activity results, it was concluded that macroporous silver monoliths can serve as efficient disinfection agents. The enhanced antibacterial properties of macroporous silver monoliths was possibly due to high surface free energy of the surface Ag+ atoms leading to cell membrane damage followed by cell death.