The Nevirapine (NVP)/Polycaprolactone (PCL)/Nanoparticles hybrids systems have been developed as a potential platform for drug delivery, by solvent cast, as thin films. NVP, an antiretroviral drug, was included within PCL matrix containing three types of nanoparticles: an organoclay layered silicate Viscogel S7® (3% w/w), hydrophilic silica oxide particles Aerosil® A20 (0.25% w/w) and titanium dioxide particles (0.25% w/w). These systems were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), low-field nuclear magnetic resonance (NMR), ultraviolet-visible spectroscopy (UV), in-vitro dissolution testing and drug release mechanism kinetics. The PCL crystallization was affected by NVP incorporation, modifying its semi-crystalline structure to a less ordered structure. When nanoparticles and NVP were added, the T 1 H values increased, for PCL, PCL/S7, PCL/ SiO 2 and PCL/TiO 2 hybrids, suggesting that its addition produced a new material, with less molecular mobility, due to the new intermolecular interactions formation. It can consider a structure formation among the PCL chains, nanoparticles and NVP, with strong forces in the PCL/SiO 2 /NVP system. The amount of NVP included was around 1.5 ± 0.03 mg/cm 2. In the in-vitro dissolution test, the PCL/SiO 2 /NVP system released the smallest amount of drug and this result could be attributed to the strong intermolecular interaction between the drug and the PCL/SiO 2 system. Higuchi's model was the mathematical model chosen to treat the release data, since this model presented the highest coefficient correlation (r) value. The drug release probably occur by diffusion through the matrix pores, thus, these materials are suitable for sustained release of NVP.