Green nanoparticle synthesis has been achieved using environmentally acceptable plant extract and ecofriendly reducing and capping agents. The present study was carried out to establish the larvicidal activity of synthesized silver nanoparticles (AgNPs) using leaf extract of Nerium oleander (Apocynaceae) against the first to fourth instar larvae and pupae of malaria vector, Anopheles stephensi (Diptera: Culicidae). Nanoparticles are being used in many commercial applications. It was found that aqueous silver ions can be reduced by the aqueous extract of the plant parts to generate extremely stable silver nanoparticles in water. The results were recorded from UV-Vis spectrum, Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX) spectroscopy analysis. The production of the AgNPs synthesized using leaf extract of N. oleander was evaluated through a UV-Vis spectrophotometer in a wavelength range of 200 to 700 nm. This revealed a peak at 440 nm in N. oleander leaf extracts, indicating the production of AgNPs. The FTIR spectra of AgNPs exhibited prominent peaks at 509.12 cm(-1) (C-H bend alkenes), 1,077.05 cm(-1) (C-O stretch alcohols), 1,600.63 cm(-1) (N-H bend amines), 2,736.49 and 2,479.04 cm(-1) (O-H stretch carboxylic acids), and 3,415.31 cm(-1) (N-H stretching due to amines group). An SEM micrograph showed 20-35-nm-size aggregates of spherical- and cubic-shaped nanoparticles. EDX showed the complete chemical composition of the synthesized nanoparticles of silver. Larvicidal activity of aqueous leaf extract of N. oleander and synthesized AgNPs was carried out against Anopheles stephensi, and the results showed that the highest larval mortality was found in the synthesized AgNPs against the first to fourth instar larvae and pupae of Anopheles stephensi with the following values: LC(50) of instar larvae 20.60, 24.90, 28.22, and 33.99 ppm; LC(90) of instar larvae 41.62, 50.33, 57.78, and 68.41 ppm; and LC(50) and LC(90) of pupae 39.55 and 79.10 ppm, respectively. The aqueous leaf extract exhibited larval toxicity against the first to fourth instar larvae and pupae of Anopheles stephensi with the following values: LC(50) of instar larvae 232.90, 273.71, 318.94, and 369.96 ppm; LC(90) of instar larvae 455.95, 563.10, 639.86, and 730.30 ppm; and LC(50) and LC(90) of pupae 426.01 and 805.13 ppm, respectively. The chi-square value was significant at p < 0.05 level. The possible larvicidal activity may be due to penetration of nanoparticles through a membrane. The results could suggest that the use of plant N. oleander to synthesize silver nanoparticles is a rapid, environmentally safer, and greener approach for mosquito control. This could lead us to a new possibility in vector-control strategy.