The large-scale application of volatile and highly water-soluble pesticides to guarantee crop production can often have negative impacts on the environment. The main loss pathways are vapor drift, direct volatilization, or leaching of the active substances. Consequently, the pesticide can either accumulate and/or undergo physicochemical transformations in the soil. In this scenario, we synthesized alginate nanoparticles using an inverse miniemulsion template in sunflower oil and successfully used them to encapsulate a hydrophilic herbicide, i.e., dicamba. The formulation and process conditions were adjusted to obtain a unimodal size distribution of nanohydrogels of about 20 nm. The loading of the nanoparticles with dicamba did not affect the nanohydrogel size nor the particle stability. The release of dicamba from the nanohydrogels was also tested: the alginate nanoparticles promoted the sustained and prolonged release of dicamba over ten days, demonstrating the potential of our preparation method to be employed for field application. The encapsulation of hydrophilic compounds inside our alginate nanoparticles could enable a more efficient use of pesticides, minimizing losses and thus environmental spreading. The use of biocompatible materials (alginate, sunflower oil) also guarantees the absence of toxic additives in the formulation.