Due to their widespread use in agriculture as well as in urban areas, agricultural chemicals are globally some of the most commonly encountered substances in waters. The objective of this study is to develop (including preparation and characterization) a new modified release system for the herbicide atrazine, employing poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) microspheres. The microspheres were prepared by the emulsification/solvent evaporation method, emulsifying an organic phase (atrazine and PHBV dissolved in chloroform) into an aqueous phase containing polyvinyl alcohol (PVA) as surfactant, under stirring, and then evaporating the solvent. A 2(4-1) fractional factorial design, investigating the influence of four variables at two levels, was performed to obtain formulations with optimized association efficiencies. There was a greater dependence of association efficiency on PVA concentration (negative) and the mass of polymer (positive) with lesser influence of both stirring speed and organic phase volume. The size of the particles was assessed using scanning electron microscopy, which showed that the particles were rough-surfaced spheres. The results obtained are promising, since the formulations presented encapsulation efficiency near 25% and the release kinetics profile of atrazine was altered when it was encapsulated in the microparticles, indicating that these systems may be efficient in reducing the environmental impact caused by the herbicide, hence making it safer to use.