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Pesticides are essential to contemporary agriculture and are required to safeguard plants from hazardous pests, diseases, and weeds. In addition to harming the environment, overusing these pesticides causes pests to become resistant over time. Alternative methods and agrochemicals are therefore required to combat resistance. A potential solution to pesticide resistance and other issues may be found in nanotechnology. Due to their small size, high surface-area-to-volume ratio, and ability to offer novel crop protection techniques, nanoformulations, primarily biopolymer-based ones, can address specific agricultural concerns. Several biopolymers can be employed to load pesticides, including starch, cellulose, chitosan, pectin, agar, and alginate. Other biopolymeric nanomaterials can load pesticides for targeted delivery, including gums, carrageenan, galactomannans, and tamarind seed polysaccharide (TSP). Aside from presenting other benefits, such as reduced toxicity, increased stability/shelf life, and improved pesticide solubility, biopolymeric systems are also cost-effective; readily available; biocompatible; biodegradable; and biosafe (i.e., releasing associated active compounds gradually, without endangering the environment) and have a low carbon footprint. Additionally, biopolymeric nanoformulations support plant growth while improving soil aeration and microbial activity, which may favor the environment. The present review provides a thorough analysis of the toxicity and release behavior of biopolymeric nanopesticides for targeted delivery in precision crop protection.