Microbial contamination remains a global issue threatening human health. In this research, silver nanoparticles (AgNPs) were fabricated using Osmanthus fragrans flower extract as a reducing agent, and biochar derived from carbonizing waste barley distillers’ grain shells was used as a support to fabricate silver-loaded carbon (C-AgNP, C-Ag). PVA-CS-C-Ag-St gel was acquired by cross-linking polyvinyl alcohol (PVA), chitosan (CS), and starch (St) with glutaraldehyde (GA). Results from SEM, FTIR, and XRD demonstrated that PVA, CS, St, and C-Ag were successfully incorporated into the gel. The PVA-CS-C-Ag-S gel showcased excellent swelling and water retention properties, which had substantial antibacterial activity against Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, with inhibition zones of 25.0 mm, 22.5 mm, and 18.0 mm, respectively. Finally, the antimicrobial analysis revealed that PVA-CS-C-Ag-St gel exhibited excellent antimicrobial properties against typical Gram-positive bacteria (Staphylococcus aureus) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Overall, the PVA-CS-C-Ag-St gel holds great promise for food preservation and environmental pollution control.