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Although Ag-based materials are efficient against antibiotic-resistant bacteria, their high toxicity to living organisms represents a major challenge for obtaining useful products. In this work, we report the bactericidal activity of Ag 4 V 2 O 7 /β-AgVO 3 heterostructures, which proved to be effective against Klebsiella pneumoniae (ATCC 1706, a standard strain; A54970, a multidrug-resistant carbapenemase (KPC)-producing strain; A34057, a multidrug-resistant strain capable of producing extended spectrum beta-lactamases (ESBL); and a community-isolated strain, A58240) at minimum inhibitory concentrations (MIC) as low as 62.5 μg/mL. This activity is higher than that reported for the individual silver vanadates (Ag 4 V 2 O 7 or β-AgVO 3 ) owing to the synergistic interactions between both semiconductors. However, the most efficient heterostructure was found to be toxic to mouse 3 T3 fibroblasts and to L. sativa and C. sativus seeds, as indicated by MTT ((4,5 - dimethylthiazol -2yl) 2,5 -diphenylbromide), neutral red assays and germination index measurements. The antimicrobial, phytotoxic and cytotoxic activities were all associated with an efficient generation of reactive oxygen species (ROS) in the heterostructure, especially OH and O 2 - radicals. The ROS production by Ag 4 V 2 O 7 /β-AgVO 3 heterostructures was measured through photodegradation studies with Rhodamine B. While the bactericidal activity of the heterostructures is promising, especially when compared to Ag-based materials, their use in practical applications will require encapsulation either to avoid leaching or to mitigate their toxicity to humans, animals and plants., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)