In this study, the preparation and characterization of haloxyfop-R-methyl herbicide loaded in poly(methylmethacrylate) (PMMA) nano-capsules by emulsion polymerization and its release behavior were investigated. The chemical characterizations of PMMA/haloxyfop-R-methyl nano-capsules were confirmed by FT-IR spectroscopy method, and the surface morphology was studied by field emission scanning electron microscopy and transmission electron microscopy. Also, the herbicide loading and encapsulation efficiency were analyzed for the herbicide-loaded nano-capsules. The release rate of PMMA/haloxyfop-R-methyl nano-capsules was determined by UV-visible spectroscopy. The thermal properties and thermal stability of nano-capsules were explored by the thermal gravimetric analysis method. The diameter of the nano-capsules was in the range of 100–300 nm. Increasing the amount of herbicide in nano-formulations significantly affected the surface of the nano-capsules and reduced their surface smoothness. Triton-X100 was identified as the best surfactant for the preparation of nano-capsules, and the sample containing the lowest herbicide content showed the best performance in terms of encapsulation and loading efficiency. This sample showed a steady-state release rate during the six days.