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Polypropylene/titanium dioxide (PP/TiO2) nanocomposites can be prepared using a novel method based on the hydrolysis–condensation reactions (sol–gel method) of titanium alkoxide inorganic precursors that have been premixed with polypropylene under molten conditions. The resultant nanocomposites were characterised by transmission electronic microscopy (TEM), X-ray diffraction, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). These techniques showed the formation of the titanium oxi-hydroxide chemical structure (TixOy(OH)z) with a diameter of approximately 10 nm in the polymer matrix. Furthermore, a condensation degree of around 17% was determined using XPS analysis. The antibacterial activity was tested according to the JIS Z 2801:2000 standard with Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli) in the absence of light. Correlations between the microstructure and the chemical composition of PP/TiO2 nanocomposites and the antibacterial properties of these nanocomposites were discussed. The structure of titanium oxi-hydroxide derivative particles (TixOy(OH)z) within the polypropylene matrix has been shown to impact strongly on the antibacterial properties in comparison with the results obtained with a dispersion of anatase titanium dioxide into the PP.