The hydrophobic functionalization of cotton-based fabrics has been achieved through a non-fluorinated sol–gel route. This functionalization is based on the dilution of a hexadecyl-modified (C16) alkoxide within a sol–gel derived crystalline suspension (CS) of titanium oxide in liquid solution. This latter suspension exhibits excellent stability, which allows the preparation of mixed C16-TiO₂ sols using a same CS over a long period of time. Mixed sols can then be impregnated on various kinds of substrates, including textile fabrics. Fourier transform infrared spectroscopy, as well as optical, atomic force, and scanning electron microscopy, have been used to study chemical and morphological features arising from such sols. Wettability measurement are then presented and discussed in relation to chemical and morphological features. It is shown that this sol–gel route flexibly yields a marked hydrophobic behavior on cotton-based textile fabrics.