A low-temperature route to directly obtain polymer/titania hybrid films is presented. For this, a custom-made poly(3-alkoxy thiophene) was synthesized and used in a sol-gel process together with an ethylene-glycol-modified titanate (EGMT) as a suitable titania precursor. The poly(3-alkoxy thiophene) was designed to act as the structure-directing agent for titanium dioxide through selective incorporation of the titania precursor. The nanostructured titania network, embedded in the polymer matrix, is examined with atomic force microscopy (AFM) and scanning electron microscopy (SEM) measurements. By means of the scattering technique grazing incidence wide-angle X-ray scattering (GIWAXS), a high degree of crystallinity of the polymer as well as successful transformation of the precursor into the rutile phase of titania is verified. UV/Vis measurements reveal an absorption behavior around 500 nm which is similar to poly(3-hexyl thiophene), a commonly used polymer for photoelectronic applications, and in addition, the typical UV absorption behavior of rutile titania is observed.