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Titanium dioxide/poly(&#948;-valerolactone) (TiO₂/P&#948;-VL) nanohybrid material containing interconnected pores with sizes in the range 80&#8315;150 &#956;m were prepared by the solvent casting and polymer melting routes, and the dispersion of the TiO₂ nanofiller in the P&#948;-VL matrix and its adhesion were characterized by X-ray diffraction, differential scanning calorimetry, and scanning electron microscopy. A significant depression in the glass transition temperature (<i>T_g</i>) and melting temperature (<i>T_m</i>) values were revealed for the polymer nanocomposites prepared by the solvent casting technique. For the potential application of the prepared materials in the biomedical domain, complementary analyses were performed to examine the dynamic mechanical properties, and cell adhesion (using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay), and the results obtained for the samples prepared by the two methods were compared. Interconnected pores were successively produced in the new material by employing naphthalene microparticles as a porogen for the first time, and the results obtained were very promising.