The influence of the plasticizer content and film preparation procedure on the morphology, density, thermal and mechanical properties of cellulose acetate (CA) films plasticized with poly-(caprolactone triol) (PCL-T), were studied. Differential scanning calorimetry (DSC), thermal mechanical analysis (TMA), scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and infrared spectroscopy (FT-IR) techniques were used. The films were prepared by dry-casting CA and CA/PCL-T in acetone or acetone/water solutions, which produced transparent and opaque films, respectively. In contrast to the transparent films, which were dense, the opaque films presented a porous morphology. However, the presence of PCL-T reduced the opaque film porosity, increasing, in consequence, its bulk density. The TMA results revealed that PCL-T reduced the glass transition temperature more significantly in the transparent than in opaque films. Only the transparent CA/PCL-T films presented a melting temperature, that reduced with higher concentrations of PCL-T, suggesting a higher ordering (crystallinity) when the films were prepared in the absence of water, as observed from WAXD curves. The mechanical properties also showed that the transparent films were more soft and tough than the opaque films. In summary, PCL-T was a good plasticizer agent for CA films due to the presence of hydrogen bonds between the components (FT-IR spectra). The presence of water in the dry casting process has a significant effect mainly on film morphology and mechanical properties.