The use of the polymer/drug combination in additive manufacturing involves filament production through hot melt extrusion (HME). Atorvastatin (ATV) has diverse effects, including bone anabolism and cardiovascular improvements. This study compares the addition of ATV to polycaprolactone (PCL) and polylactic acid (PLA). Filaments of PCL/ATV and PLA/ATV were produced through HME and characterized by Scanning Electron Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS), Raman, Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD), and Small-Angle X-ray Scattering (SAXS). ATV release was assessed using UV-Vis. The EDS analysis confirmed the presence of ATV in the filament, despite it not being possible, based on surface morphology, to distinguish between polymer and drug, which indicates good dispersion of ATV in the polymeric matrix. FTIR, RAMAN, XRD, and SAXS analyses reveal ATV's distinct interactions with PLA and PCL. FTIR highlights ATV's stronger interaction with PLA, while Raman indicates changes in PLA, they are less pronounced than in PCL. The XRD shows PLA's amorphous nature compared to PCL semi crystallinity nature. XRD suggests potential ATV amorphization in PLA_ATVf (filaments), while PCL_ATVf shows a decrease in crystallinity compared to PCL. HME's effect on ATV is essential. Despite ATV's crystallinity in PCL-ATVf by XRD, its release resembles PLA_ATVf. At the eighth hour, ATV release from PCL_ATVf was 12% higher than from PLA_ATVf. The data fitted the Korsmeyer-Peppas model.