This work reports the synthesis of new polymer-titania hybrids, where the organic phase is constituted by polyesters such as poly(-caprolactone), poly(d,l-lactic acid), and poly(l-lactic acid). In these hybrids, very strong interaction between the organic and inorganic domains is obtained through transesterification of ester moieties by titanium atoms, which leads to organotitanium esters. The influence of the structure of the polyester on the mode of its interaction with titania is also investigated. Hybrids with a range of solid-state properties, which depend on the starting polymer characteristics and on the inorganic-phase content, are obtained. Hybrids are applied as coatings on a variety of substrates. They show intrinsic optical transparency and the ability to completely block UV radiation in the range UVB and UV-A2. In particular, when applied to different textiles, the hybrids impart radiopacity to the fabrics, opening new perspectives in the field of personal protective clothing and equipment.