The development of novel mosquito control tools is a key prerequisite to build effective and reliable Integrated Vector Management strategies. Here, we proposed a novel method using cigarette butts for the synthesis of Ag nanostructures toxic to young instars of the malaria vector Anopheles stephensi, chloroquine (CQ)-resistant malaria parasites Plasmodium falciparum and microbial pathogens. The non-target impact of these nanomaterials in the aquatic environment was evaluated testing them at sub-lethal doses on the predatory copepod Mesocyclops aspericornis. Cigarette butt-synthesized Ag nanostructures were characterized by UV–vis and FTIR spectroscopy, as well as by EDX, SEM and XRD analyses. Low doses of cigarette butt extracts (with and without tobacco) showed larvicidal and pupicidal toxicity on An. stephensi. The LC50 of cigarette butt-synthesized Ag nanostructures ranged from 4.505 ppm (I instar larvae) to 8.070 ppm (pupae) using smoked cigarette butts with tobacco, and from 3.571 (I instar larvae) to 6.143 ppm (pupae) using unsmoked cigarette butts without tobacco. Smoke toxicity experiments conducted against adults showed that unsmoked cigarette butts-based coils led to mortality comparable to permethrin-based positive control (84.2 and 91.2%, respectively). A single treatment with cigarette butts extracts and Ag nanostructures significantly reduced egg hatchability of An. stephensi. Furthermore, the antiplasmodial activity of cigarette butt extracts (with and without tobacco) and synthesized Ag nanostructures was evaluated against CQ-resistant (CQ-r) and CQ-sensitive (CQ-s) strains of P. falciparum. The lowest IC50 values were achieved by cigarette butt extracts without tobacco, they were 54.63 μg/ml (CQ-s) and 63.26 μg/ml (CQ-r); while Ag nanostructure IC50 values were 72.13 μg/ml (CQ-s) and 77.33 μg/ml (CQ-r). In MIC assays, low doses of the Ag nanostructures inhibited the growth of Bacillus subtilis, Klebsiella pneumoniae and Salmonella typhi. Finally, the predation efficiency of copepod M. aspericornis towards larvae of An. stephensi did not decrease in a nanoparticle-contaminated environment, if compared to control predation assays. Overall, the present research would suggest that an abundant hazardous waste, such as cigarette butts, can be turned to an important resource for nanosynthesis of highly effective antiplasmodials and insecticides.