Abstract Mangosteen pericarp contains a lot of α-mangostin compounds which has very high antioxidant activity. Unfortunately, it has a low solubility in aqueous solution in which for drug delivery application. This paper reports the synthesis of polyvinylpyrrolidone (PVP) nanoparticles loaded with mangosteen pericarp extract (MPE) using the ES method. PVP was trusted as a hydrophilic matrix to carry MPE. The composition of the precursor solution and solution flow rate during the ES process were varied to control the formation of PVP/MPE composite nanoparticles. PVP/MPE composite particles obtained have some wrinkles on their surface and have a geometric average diameter range of 640 to 1534 nm with a geometric standard deviation of 1.35 to 1.65. Increasing the electrical conductivity of the precursor solution resulted in a decrease of nanoparticles' average diameter. Also, the greater the flow rate, the larger the particles formed. The results agreed well with the droplet scaling relations for EHDA by Chen and Pui. Peak shifts in Fourier-transform infrared spectra of PVP/MPE composite nanoparticles indicated hydrogen bond formation between PVP and MPE. It also showed that MPE was successfully encapsulated in PVP matrix. Crystalline peaks of MPE disappear in the X-ray diffraction patterns of PVP/MPE composite nanoparticles, indicating amorphization of MPE after being electrosprayed by PVP. The differential scanning calorimetry study confirmed a hygroscopicity of PVP. The thermogram shows a broad endothermic peak from around 50 to 100 °C as a result of dehydration. In this study, the use of flow rate during the electrospraying process only affected the geometric average diameter, did not change the functional groups, thermal properties, and crystallinity of PVP/MPE particles because they came from the same precursor solution. The results here demonstrate that the ES method can be used for polymeric-nanoparticle-composite production and as an innovation in the field of drug delivery application.