Polydimethylsiloxane-α,ω-diol was used as matrix for the preparation of polysiloxane-SiO2-TiO2 composites through in situ incorporation of silica and titania using a solvent-free sol-gel procedure. For this purpose, oxide precursors tetraethyl-orthosilicate and tetrabutyl-orthotitanate, and a proper condensation catalyst, viz. dibuthyltin dilaurate, were added in pre-established amounts to the polymer. The hydrolysis and condensation reactions take place under mild conditions, with the formation of silicon and titanium oxide networks and polymer crosslinking. The effect of SiO2 and TiO2 mass ratio on the morphology of the composites was investigated by scanning electron microscopy (SEM) and X-rays diffraction (XRD), and interpreted in correlation with differential scanning calorimetry (DSC) and energy-dispersive X-ray spectroscopy (EDX) data. The film samples were tested as active elements in actuation devices.