A green and scalable approach for the preparation of few-layered graphene utilizing the biowaste of potato peels has been developed. The potato peels have been dried and carbonized to obtain a new graphite structure that has been exfoliated in N-methylene phosphonic acid chitosan (MPC). The exfoliation process assisted the formation of graphene sheets with a high size diameter and quality of 50% based on the weight of graphite structure. The graphene sheets were green decorated with silver nanoparticles using microwave power to obtain new nanocomposites. The mass ratio between the graphite and silver nitrate was optimized and observed to change the morphology and size diameter of silver nanoparticles. The as-prepared MPC structure, graphene, and silver decorated graphene nanocomposites were characterized using 1HNMR, FTIR, XRD, UV/Vis spectrophotometer, SEM, and TEM besides tested as antimicrobial agents. The bacterial performance was also controlled by changing the number of AgNPs distributed on graphene sheets based on the mass ratios of graphite/AgNO3. The inhibition diameter of silver decorated graphene was considerably increased to 24.8, and 20.1 mm as in the case of MPC-GRP-Ag30 composite compared to the pure graphene (11.2, 13.5 mm) for E. coli and S. aureus, consecutively proposing that the blade edge of graphene sheets can destroy the bacteria membrane and release silver cations promptly that are directed for the interaction with the cytoplasmic parts of the bacteria cell. Such findings offer green and biocompatible antibacterial agents based on the graphene derived from the biowaste products.